Pars secunda - unizg.hr · Pars secunda • Adicija, eliminacija, supstitucija • Pregradnja (izomerizacija) • Prijenos naboja (oksidacija i redukcija) ... interakcija je najučinkovitija

Pars secunda

bull Adicija eliminacija supstitucija

bull Pregradnja (izomerizacija)

bull Prijenos naboja (oksidacija i redukcija)

Vrste kemijskih reakcija

Brzine nekih tipova reakcija

Glava treća

Reakcije supstitucije

Supstitucijske reakcije

supstitucija uključuje zamjenu koordiniranog liganda slobodnim ligandom u

otopini ili zamjenu koordiniranog metalnog iona slobodnim metalnim ionom

najopsežnije su istraživani oktaedarski i kvadratni kompleksi

raspon brzina obuhvaća gotovo 18 redova veličina

labilni (reaktivni) su metalni ioni ili njihovi kompleksi koji reagiraju brzo (unutar

sekundacirc)

inertne su specije u kojih se dvostruka izmjena zbiva sporo (minute ili više)

Brzina reagiranja nije povezana s termodinamičkom stabilnošću ndash nestabilni

spojevi bogu biti inertni a stabilni spojevi mogu biti labilni

Stabilno i labilno

bull Standardna konstanta nastajanja [Hg(CN)4]2- pri 25 degC je reda veličine

1041 a supstitucija CN- brza

[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-

bull Standardna konstanta nastajanja [Fe(CN)6]4- (d6) pri 25 degC reda veličine

1037 a supstitucija CN- ekstremno spora ndash tremodinamički nestabilniji

kinetički inertniji

Reaktivni i inertni ioni

Henry TaubeKompleksi Cr(III) (d3) su uglavnom inertni

[Cr(en)2(ox)]+ + 4 H2O [Cr(ox)(H2O)4]+ + 2 en spora izmjena

Kompleksi Cu(II) (d9) su uglavnom labilni

[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]

2+ + 4 H2O brza izmjena

Stabilnost je posljedica elektronske konfiguracije iona u danom

ligandnom polju ndash u oktaedarskom labilni ioni imaju prazne

niskoenergijske orbitale t2g ili popunjene visokoenergijske eg

- Objašnjava inertnost Cr(III) - t2g3 Co(III) - t2g

6 Fe(II) - t2g6 i labilnost Cr(II) - t2g

3 eg1

- Ne Objašnjava zašto je izmjena vode u Ni(II) bitno sporija nego u Co(II) i Cu(II)

Općenito vrijedi1 Svi kompleksi elemenata s-bloka su jako labilni osim najmanjih (Be2+ i Mg2+)

2 Kompleksi M(III) iona elemenata f-bloka su jako labilni

3 Kompleksi d10 iona (Zn2+ Cd2+ i Hg2+) su također vrlo labilni

4 Duž 3d serije kompleksi M(II) iona elemenata d-bloka su umjereno labilni (Cu(II) komplekse

su najstabilniji ndash okrivljuje se Jahn-Tellerov učinak) ndash Irving-Williamsov niz

5 M(III) kompleksi su stabilniji od M(II) kompleksa elemenata d-bloka

6 Kompleksi s d3 i niskospinskim d6 konfiguracijama na pr Cr(III) Fe(II) i Co(III) u nisu

labilni Kelatni kompleksi s istom konfiguracijom poput [Fe(phen)3]2+ su izrazito inertni

7 Kompleksi 4d i 5d elemenata nisu labilni a što je lsquoposljedicarsquo velike energije cijepanja

ligandnog polja i jakosti veze metal-ligand

Irving-Williamsov niz

Stabilnost u nizu dvovalentnih iona povećava se u sljedećem nizu

Ba2+ Sr2+ Ca2+ Mg2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ gt Zn2+

Porast inertnosti povezan s ionskim radijusom ndash elektrostatski efekt

Fe2+ d6 Co2+ d7 Ni2+ d8 Cu2+ d9 ndash

za jako ligandno polje - Cu(II) stabilniji od Ni(II) iako imaju elektron u

protuveznoj eg orbitali - Jahn Teller (jake veze u

ekvatorijalnoj ravnini)

Ni(CO)2L2 gtgt Cr(CO)4L2 gtgt Fe(CO)3L2

108

supstitucije karbonila

Co(CO)4 Mn(CO)5 gt V(CO)6 gt Ni(CO)4 gt Ti(CO)3(P⁀P)2 gt Cr(CO)6 gt Fe(CO)5

~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+

Ir3+ Rh3+ Cr3+ Ru3+ Al3+ Fe3+ V3+ Ti3+ In3+ Yb3+ Er3+ Dy3+

Ga3+ Tm3+ Ho3+ Tb3+

Gd3+

Pt2+ Pd2+ Zn2+ Cd2+ Hg2+

Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+

10minus8 10minus6 10minus4 10minus2 100 102 104 106 108 101010minus10

2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Brzina supstitucije vode u oktaedarskim heksaakva-kompleksima

Co(CN)5Cl3ndash + H2O rarr Co(CN)5H2O2ndash + Clndash (solvoliza)

Co(CN)5H2O2ndash + N3

ndash rarr Co(CN)5N33ndash + H2O (anacija)

Pt(dien)Br+ + Clndash Pt(dien)Cl+ + Brndash (metateza)

supstitucija je često prvi korak u kompleksnijem mehanizmu (oksidoredukciji di-

ili polimerizaciji)

Supstitucije sa zasebnim imenima

Mehanizmi supstitucije

CH Langford HB Gray Ligand Substitution Processes WA Benjamin Inc New York (1965)

MXn ∙ ∙ ∙ Y MXnminus1Y ∙ ∙ ∙ X I minus mehanizam izmjene

MXn MXnminus1 MXnminus1Y D minus disocijacijski mehanizam+Y

minusY

minusX

+X

MXn MXnY MXnminus1Y A minus asocijacijski mehanizamminusX

+X

+Y

minusY

Ali i intermedijarni mehanizmi Ia i Id

Ia I Id DA

Disocijacijski mehanizam

ML M + L k1 kndash1

M + L1 ML1 k2 kndash2

L1 u suvišku u odnosu na ML kndash2 asymp 0)

121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger

M S S M S= + -V V V V5 6M S M SltV V Vǂ lt VS

za mehanizam D u vodenoj otopini VDagger lt 18 cm3∙molndash1 (+9 do +11 cm3∙molndash1)

u mehanizmu A dolazi do nastanka međuprodukta većeg koordinacijskog broja od

reaktanta

11 LM L)(M L

kdt

d

M L + L 1 [M LL 1 ]Dagger M L 1 + Lk

M L + L 1 [M LL 1 ]Dagger M L 1 + Lkk

DaggerV će biti negativan do iznosa od oko ndash11 cm3 molndash1

Asocijacijski mehanizam

Gotovo sve supstitucije u kvadratnim kompleksima

odvijaju se asocijacijskim mehanizmom

kidanje veze određuje brzinu

Reakcijska koordinata

EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

stvaranje veze određuje brzinu


EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y

najviša energijska razina određuje glavno prijelazno stanje

Spora disocijacija MXY rarr MminusY + XBrza asocijacija MminusX + Y MXY

energija međuprodukta može biti između energija reaktanta i produkata


M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP

Za kvadratne komplekse

Kakva je geometrija pentakoordiniranih međuprodukata ili aktiviranih kompleksa

trigonskoj bipiramidi odgovara međusobna interakcija najmanje pet liganada i

dostupnih orbitala

tijekom izmjene oblikuju se geometrije kako kvadratne piramide tako i trigonske

bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E

[T D i E u trigonskoj ravnini]

u slučaju Au(III) kidanje i stvaranje veze događa se istodobno minus pentakoordinirana

specija je aktivirani kompleks i postoji samo jedan maksimum u reakcijskom profilu

slijed reaktivnosti je

Ni(II) gtgt Au(III) gt Pd(II) gt Pt(II)

slijed možda ima veze sa postojanošću pentakoordiniranih kompleksa i lakoćom s

kojom je ona postignuta u prijelaznom stanju

Mehanizam izmjene

Eigen-Wilkinsov mehanizam

bull ML + L1 ML ∙ ∙ ∙ L1 K0 brzo

bull ML ∙ ∙ ∙ L1 rarr ML1 ∙ ∙ ∙ L k3

bull ML1 ∙ ∙ ∙ L ML1 + L brzo

u mehanizmu I zamjena L i L1 možda se događa unutar kompleksa vanjske ljuske

opseg utjecaja L1 na proces k3 određuje oznaku mehanizma Id I ili Ia

010

010031

L1

LM L)(M L

K

Kk

dt

d

Pri čemu je [ML]0 je ukupna

koncenstacija kompleksacirc

Kompleks vanjske ljuske

sekundarnom interakcijom kompleksa unutarnje ljuske s ligandima u otopini nastaje

kompleks vanjske ljuske

interakcija je najučinkovitija između suprotno nabijenih specija (ionski parovi)

izraz kompleks vanjske ljuske skovao je Alfred Werner 1913

Npr adicija brojnih aniona na M(NH3)5H2O3+ (M = Cr ili Co) znatno prije nego li dođe do

konačne izmjene liganada između unutarnje i vanjske ljuske

[Co(NH3)5H2O]3+ + N3ndash [Co(NH3)5H2O]3+ ∙ ∙ ∙ N3

ndash


[Co(NH3)5N3]2+ + H2O

Kompleks unutarnje ljuske

K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0

Razlikovanje različitih

mehanizama I

DaggerV za Ia malen i negativan ndash za izmjenu vode u V2+ i Mn2+ -41 i -54 cm3∙molndash1

DaggerV za Id malen i pozitivan ndash za izmjenu vode u Co2+ i Ni2+ 61 i 73 cm3∙molndash1

DaggerV za I blizu nule

Ia Id

Za anaciju D kmj = k1k2[L] (k-1 [H2O] + k2[L]) ndash pri velikim [L] kmj([L]) nije linearna

Za anaciju Id kmj = K k [L] [M-H2O]

Klasični dokaz postojanja mehanizma D Haim i Wilmarth ndash za substituciju vode azidom u

[Co(CN)5H2O]2+ kmj([L]) nije linearna (ponovljeno mjerenje ndash ipak jest)

D vs Id

A vs Iasupstitucije u kompleksima Pt(II) i Pd(II) imaju negativne DaggerS i DaggerV - u skladu s

asocijacijskim mehanizmom

niska vrijednost DaggerV ukazuje da je mehanizam tipa Ia

Konačni dokaz za D ili A ndash prisutnost međuprodukta ndash ako se ne može dokazati

isto treba gledati druge pokazatelje

Nizak [L1] Srednji [L1] Visok [L1]

D k2[L1] lt k-1[L] k2[L1] ~ k-1[L] k2[L1] gt k-1[L]

Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon

brzinek3K0[ML]0[L1]0 k3[ML]0

121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk

Kinetičke značajke različitih mehanizama

određivanje tipa mehanizma (D I ili A) na temelju zakona brzine nije lako

za mehanizam A zakon brzine drugog reda vrijedit će za sve koncentracije L1

pri niskom [L1] svi mahanizmi ponašaju se po zakonu brzine drugog reda

U organometalnim (alkilnim kompleksima)

Supstitucija alkilnih kompleksa stehiometrijski je slična drugim supstitucijskim reakcijama

CH3Mn(CO)5 + L rarr CH3Mn(CO)4L + CO

CH3Mn(CO)5 + L rarr CH3C(O)Mn(CO)4L rarr CH3Mn(CO)4L + CO

reakcije umetanja karbonila (CO insertion) ili prijenosa (izmiještanja) alkilne skupine (alkyl

migration)

-katalizirane Lewisovim kiselinama

-koraci u mnogim (komercijalno važnim) katalitičkim procesima (hidroformilacije

karbonilacije metanola)

L

CH3

L

C

L

L

L

CH3C O

CH3

O

Izmještanje metilaUmetanje CO

Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O


LrsquoLrsquo LrsquoLrsquo

Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash 13COndash 13CO

Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25

Prijenos metilne skupine

13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13 ndash 13COndash 13COMn

CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)

Utjecaj ulazećeg i izlazećeg liganda

Najčešće se promatra reakcija

gdje su L i L1 monodentatni ligandi od kojih je jedan molekula vode

ako su aktivacijski parametri osjetljivi na promjenu ulazeće a neosjetljivi prema

izlazećoj skupini mehanizam je asocijacijski aktiviran

ML + L1 ML1 + L

Oktaedarski kompleksi

brzina asocijacijskog mehanizma ovisi o svim ligandima ndash ulazećim izlazećim i

ostalim - svi oni su prisutni u aktiviranim pentakoordiniranim kompleksima ipodjednako

utječu na njegovu stabilnost i aktivacijsku energiju nastajanja

Tetraedarski kompleksi

Učinak ulazećeg liganda

za brojne reakcije trans-Pt(py)2Cl2 s velikim brojem raznolikih liganada izmjerene su

konstante brzine reakcije

veliki raspon brzina ukazuje na asocijacijski mehanizam

za različite reakcije Pt kompleksa u različitim otapalima vrijedi

log kY = snPt + log ks

bull s minus nukleofilni diskriminacijski čimbenik

bull nPt minus konstanta nukleofilne reaktivnosti korisna je za usporedbu kinetičkih podataka

drugih kompleksa Pt(II)

NUKLEOFILNOST LIGANADA skala nPt

Skala nPt temelji se na reakciji

metanol

trans-[(py)2Pt(Cl)2] + Y trans-[(py)2Pt(Cl)(Y)]+ + Cl-

gdje je

nPt = log (ky kMeOH)

Skala vrijedi za reakcije Pt(II) približno za druge

metale ali ne vrijedi za elemente 3d serije

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10

103 k molminus1 dm3 sminus1

nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-

NUKLEOFILNOST LIGANADA

Nukleofilnost nekog liganda određuje

1 Bazičnost

- bazičnost liganda karakterizira njegova pKa vrijednost

2 Polarizabilnost

- polarizabilni nukleofilni ligand bdquomekanordquo pibližavanje centralnom metalnom ionu (ulazni ligand (nukleofil) ima lsquoprazne

orbitalersquo niske energije)

3 Lakoća oksidacije

-ligand koji se lako oksidira bolji je nukleofil (standardni redukcijski potencijal)

4 Solvatacijska energija

-ligandi koji su bolje solvatirani slabiji su nukleofili

Učinak izlazeće skupine

Pt(dien)X+ + py rarr Pt(dien)py2+ + Xndash

istraživanje učinka X na brzine reakcija u vodenoj otopini

CNndash lt NO2ndash lt SCNndash lt N3

ndash ltlt Indash lt Brndash lt Clndash lt H2O lt NO3ndash

članovi niza razlikuju se u k za faktor 106 od najniže (CNndash) do najviše

konstanta brzine 2 reda povećava se sa smanjenjem bazičnosti izlazeće skupine

kidanje veze metal-ligand ipak igra važnu ulogu iako je mehanizam asocijacijski

Disocijacija karboksilatnih liganada

U slučaju disocijacije monodentatno vezanih karboksilatnih liganada postoje dva

moguća mjesta pucanja veze

U slučaju metalnih iona koji stvaraju labilne komplekse u pravilu puca a

U slučaju metala koji stvaraju inertne komplekse može pucati bilo koja veza (ili

obje) ovisno o R (npr u kompleksima Co(NH3)5CO2R solvoliza s izotopno

obilježenom vodom pokazuje da za R = CH3 puca a ali za za R = CF3 puca b)

Slično se ponašaju i drugi višeatomni ligandi (organski i anorganski s kisikom kao

donornim atomom (sulfati fosfati)

M O

O

R

a

b

Učinak prisutnih liganada ndash kontrola stereokemije produkta

skupina trans prema izlazećem ligandu ima izraženiji utjecaj na brzinu izlaska od

dviju cis skupina

ligandu se može pripisati red trans učinka

trans učinak minus usmjeravanje ulazeće skupine u položaj trans u odnosu na ligand

smanjenje moći trans učinka za komplekse Pt(II)

CNndashC2H4CONO gt R3P asymp Hndash asymp SC(NH2)2 gt CH3ndash gt C6H5

ndash gt

gt SCNndash gt NO2ndash gt Indash gt Brndash gt Clndash gt NH3 gt OHndash gt H2O

veći trans učinak ima za posljedicu veće konstante brzine za uklanjanje trans liganda

skupine s izraženom težnjom trans labilizaciji zamjenjuju se najteže

u pentakoordiniranom međuproduktu ulazeći nukelofil trans ligand te izlazeći ligand

zauzimaju položaje u trigonskoj ravnini i svi mogu utjecati na energiju prijelaznog

stanja na sličan način

Trans-učinak

NA KVADRATNIM KOMPLEKSIMA

Stereokemija supstitucija na kvadratnim kompleksima zadržava

geometriju što upućuje na trigonsko piramidalno prijelazno stanje

cis-kompleks cis-produkt

transndashkompleks trans-produkt

OBRAZLOŽENJE ulazna i izlazna skupina međusobno trans u trigonskoj ravnini

Stereokemija supstitucije na kvadratnim kompleksima

(a) (b) (c) zadržavanje stereokemije

(b) (d) (e) životni vijek međuprodukta dovoljno dug i može doći do pseudorotacije

što dovodi do nastanka izomeracirc

u cis položaju prema T u trigonskoj ravnini ndash međuprodukt izlazak liganda (KB-5

4) korak koji određuje brzinu

Na metalnim karbonilima

stereokemija disocijacije CO na kompleksima s neekvivalentnim CO

skupinama

reakcije izmjene na Mn(CO)5Br

supstitucijskom reakcijom uvijek nastaje cis-Mn(CO)4LBr

supstitucijske reakcije ne ukazuju na stereokemiju disocijacije

reakcije izmjene odražavaju se na disocijacijsko mjesto

[načelo mikroskopske reverzibilnosti]

CO cis prema Br disocira najlakše

CO cis prema Br je trans prema (drugom) CO minus dijele iste p elektrone

CO trans prema Br treba biti čvršće vezan

karbonili cis prema Br disociraju mnogo brže od onih trans prema Br

(npr reakcije cis-Mn(CO)4LBr [L = PPh3 P(OPh)3 Py] ndash uvijek disociraju

karbonili cis i prema L i prema Br

Sterički zahtijevnje skupine u cis-položaju prema izlaznoj stupini mogu ometati

supstituciju i time usporavati reakciju

povećanje steričkg ometanja u kompleksima u slučaju asocijacijskog mehanizma

dovodi do smanjenja brzina (Pd(R5dien)Cl+ + Indash rarr Pd(R5dien)I+ + Clndash

prostorno ometani kompleksi [i s Pt(II) i Au(III)] sliče oktaedarskim analozima te su

nazvani pseudo oktaedarskim kompleksima glomazni ligandi u ravnini

tetrakoordiniranog metalnog kompleksa i zastru apikalne položaje zbog čega su slični

oktaedarskim kompleksima prema značajkama reaktivnosti dok istodobno zadržavaju

neke značajke kvadratnih kompleksa

L = piridin 2-metilpiridin 26-dimetilpiridin

krs-1 8middot10-2 20middot10-4 10middot10-6

Zamjena Cl- s H2O u cis-[PtLCl(PEt3)2] pri 25degC

Cis-učinak

Utjecaj otapala

solvatacija osnovnog i aktiviranog stanja ima utjecaj na energije aktivacijskih procesa

Može sudjelovati kao nukleofil

utjecaj na iznos k opažen u otapalima sposobnim snažno se koordinirati na metal

(CH3)2SO gt MeNO2 H2O gt ROH

slijed nukleofilnosti ne mijenja se u različitim otapalima

Solvolitička supstitucija (prvo se ligand supstituira molekulom otapala a u drugom

koralu ona ulaznim ligandom)

Ubrzana supstitucija monodentatnih liganada

H+ OHndash metalni ion i liganad mogu promijeniti brzinu supstitucije liganda

ovi reagensi ili mijenjaju građu reaktanata ili izravno sudjeluju u prijelaznom stanju

ovi reagensi potiču druge reakcijske tokove

ako reagens nije potrošen u reakciji ubrzavajući se učinci smatraju katalitičkim

u protivnom reagens ubrzava ili potiče reakciju

Uklanjanje potpomognuto s H+

uklanjanje liganada koji zadržavaju određenu bazičnost čak i kada su koordinirani

potpomognuto je kiselinom ndash protoniranje liganda čini ga lsquoboljom izlaznom skupinomrsquo

CrX2+ + H+ CrXH3+ K

CrX2+ + H2O rarr Cr3+ + Xndash k0

CrXH3+ + H2O rarr Cr3+ + HX k1

2+ 3+

2+ 3+

obs

CrX + CrXH- = CrX + CrXH

dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K

nastaje li znatna količina CrXH3+ [X = CH3CO2ndash] vrijedi potpuni zakon brzine

vrijedi li K ≪ [H+]kobs = k0 + k1K[H+]

Postoje iznimke (npr Fe(phen)2(CN)2 ndash manje koncentracije kiseline kataliziraju

izmjenu ali veće je inhibiraju)

Uklanjanje potpomognuto metalnim ionima

metalni ioni mogu se ponašati vrlo slično protonu

uklanjaju li se ligandi ubrzano s H+ gubitak je pripomognut i metalnim ionom

metalni ioni ubrzano uklanjaju liganade koji mogu premostiti između dva metalna

iona (NCSndash Clndash)

tvrdi metalni ioni (Be2+ Al3+) često uklanjaju tvrde ligande (Fndash)

meki metalni ioni (Hg2+ Ag+) najučinkovitiji su s mekim izlazećim ligandom (Clndash Brndash)

većinu induciranih akvacija slijedi jednostavna kinetika drugog reda

v

2+ III

2+

1

Hg Co=

1+ Hg

a

K

cis-Co(en)2Cl2+ + Hg2+ Co(en)2Cl2Hg3+

cis-Co(en)2(H2O)Cl22+ + HgCl+

K1

k2

k3



K1K1

k2

k3k3

(eksperimentalno nemoguće razlikovati)

Npr

Uklanjanje potpomognuto ligandom

anioni pospješuju hidrolizu kompleksnih kationa stvaranjem ionskih parova

povišene reaktivnosti

ligandi ubrzavaju uklanjanje koordiniranih liganada ulazeći u koordinacijsku ljusku

metala čineći ih time osjetljivim prema hidrolizi

disocijacijski mehanizam i značajno ubrzanje pospiješeni su s pomoću CH3 CNndash

SO32ndash i drugim skupinama na kompleksima Cr(III) Co(III) i Pt(IV)

monodentatni ligandi ponekad se oslobađaju tek na koncu reakcije

unutarmolekulski prijenos protona s jednog liganda na drugi u međuproduktu(ima)

obično se ligand javlja i u reaktantu i produktu

M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +

Uklanjanje potpomognuto bazom

OHminus ion može utjecati na reaktivnost sustava u kiseloj sredini

utjecaj hidroksidnog iona na reaktant vjerojatno je najvažnija u bazom

potpomognutoj hidrolizi metalnih amina i aminskih kompleksa

najviše istraživanja napravljeno je s kompleksima CoIII

Co(NH3)5X2+ + OHndash rarr Co(NH3)5OH2+ + Xndash

v = kOH[CoIII][OHndash]

zakon vrijedi sve do c(OHminus) = 1 molL nakon čega se proces jako ubrza

Moguće objašnjenje Mehanizam konjugirane baze Dcb

brza predravnoteža uz stvaranje supstitucijski nepostojanog amidnog kompleksa

(trans-učinak liganda NH2)

Co(NH3)5X2+ + OHndash Co(NH3)4(NH2)X

+ + H2O k1 kndash1 K1

Slijedi disocijacija liganda vezanje molekule vode i unutramolekulsku prijenos

protona

Co(NH3)4(NH2)X+ rarr Co(NH3)4NH2

2+ + Xndash k2

Co(NH3)4NH22+ + H2O rarr Co(NH3)4(NH2)H2O

2+ brzo

Co(NH3)4(NH2)H2O2+ rarr Co(NH3)5OH2+ brzo

[Co(NH3)5OH2+ + H2O Co(NH3)4(NH2)H2O3+ + OHndash ]

III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k

Trovalentni metalni ioni

zamjena otapala na CrIII FeIII RuIII i GaIII u vodi je drugog reda s konstantom brzine

ksup = a + b[H+]ndash1

dolazi se do podaka o supstituciji za M(H2O)63+ i M(H2O)5OH2+

negativni DaggerV ukazuju na A i Ia mehanizam za prijelazne metalne ione tipa [M(H2O)6]3+

disocijacijski mehanizam Id za ione M(H2O)5OH2+

OHndash u M(H2O)5OH2+ jako labilizira H2O u trans-položaju

deprotonacija molekule vode povećava brzinu 102 ndash 103 puta

Supstitucije koje uključuju polidentatne ligande

MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2

Uz predpostavku staljenog stanja za međuprodukt s LndashL kao monodentatnim

ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k

stvaranje prve veze pri kelataciji obično određuje brzinu reakcije

[vrijedi podjednako pri kvadratnoj i oktaedarskoj supstituciji]

H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl

54 x 10ndash3 Mndash1sndash1

H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N

H3N54 x 10ndash4 Mndash1sndash1

2++

+ NH3

H3N

Pt

Cl

NH3Cl

54 x 10ndash3 Mndash1sndash154 x 10ndash3 Mndash1sndash1

H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1

bull kf = k1 minus brzina stvaranja kelata određena je brzinom nastajanja jedinke MndashLndashL

očekuje se da je prvo stvorena veza razmjerno jaka

kidanje veze u međuproduktu (kndash1) manje je izraženo od zatvaranja prstena (k2)

Primjer

Cr(H2O)63+ + H3N

+CH2CO2ndash [Cr(H2O)6

3+H3N+CH2CO2

ndash] rarr [Cr(H2O)4H2NCH2CO2]2+

rds je izbacivanje molekule vode iz koord ljuske Cr(III) uz brzo zatvaranje prstena

k2≪ kndash1

bull kf = k1k2kndash1

rds je zatvaranje prstena

obično uzrokovano specifičnim razlozima

1 prvi korak neuobičajeno brz

Co(tren)(OH)H2O2+ + CO2 rarr Co(tren)(H2O)OCO2H

2+ rarr Co(tren)CO3+ + H3O

+

prvi je korak brz zbog toga jer ne dolazi do kidanja veze CondashO - nakon toga

slijedi sporija unutarmolekularna kelatacija

Uobičajen mehanizam supstitucije O-donornih liganada na inertnim kompleksima

(navlast Cr(III) i Co(III))

OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+

poteškoće pri zatvaranju prstena zbog kidanja unutarnje vodikove veze

Ni2+ + dnsa2ndash minus k = 31 x 104 Mndash1sndash1 (25 degC I = 03 M)

Ni2+ + dnsaHndash minus k = 38 x 102 Mndash1sndash1

O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k

2 zatvaranje prstena je ometano

stvaranjem šesteročlanih kelatnih prstenova s diketonima ili

b-aminokiselinama ndash ligand se mora deprotonirati da bi se prsten mogao zatvoriti

posebno problem ukoliko postoji unutarmolekulska vodikova veza u molekuli liganda

Učinak [H+] na brzinu supstitucije u kelatnim kompleksima

brzina nastajanja i brzina hidrolize kelata često ovisi o pH

kelatirajući ligand L i njegov monoprotonirani oblikom LH+ postoje kod pojedinog pH

čije se reaktivnosti razlikuju

HL+ H+ + L K1

M + L ML k2 kndash2 K2

M + LH+ ML + H+ k3 kndash3 K3

[K3 = K1K2 ndash za slabo kisele ligande K2 gtgt K3 budući da je K1 ltlt 1]

proton može pomoći pri uklanjanju kelatirajućeg liganda

M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X

bull koordinacijske lančane reakcije

potpuna zamjena

MA2 + NB2 rarr MB2 + NA2

miješane specije

MA2 + NB2 MAB + NAB

lančani mehanizam u kojem postoji solvatirani monokelatni međuprodukt

Oksidacijske adicije i redukcijske eliminacije

S ligandom dolazibiva uklonjen i naboj

Tipični primjeri ndash reakcije organometalnih spojeva s elementarnim halogenima

RminusX + Mg rarr RminusXbullminus + Mgbull+

RminusXbullminus rarr Rbull + Xminus

Rbull + Mgbull+ rarr RMg+

RMg+ + Xminus rarr RMgX

Franccedilois Auguste Victor Grignard

R(HgOAc)COAc + Br2 rarr RBrCO2CH3 + BrHgOAc

Hofmann-Sandova reakcija

Simmons-Smithova reakcija

bull Adicija eliminacija supstitucija

bull Pregradnja (izomerizacija)

bull Prijenos naboja (oksidacija i redukcija)

Vrste kemijskih reakcija


Glava treća








sekundacirc)




Stabilno i labilno



[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-








[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














Glava treća








sekundacirc)




Stabilno i labilno



[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-








[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Glava treća








sekundacirc)




Stabilno i labilno



[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-








[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB



















sekundacirc)




Stabilno i labilno



[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-








[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Stabilno i labilno



[Hg(CN)4]2- + 13CN- [Hg(CN)3

13CN]2- + CN-








[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB

















[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]







3 eg1





















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
































108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB






















108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














108



~1010

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk

Li+ K+ Cs+

Na+ Rb

Be2+ Mg2+ Ca2+ Ba2+

Sr2+ Eu2+


Ga3+ Tm3+ Ho3+ Tb3+

Gd3+


Mn2+ Cu2+

Ru2+ V2+ Ni2+ Co2+ Fe2+ Cr2+


2

-1H Osk







ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB


















ili polimerizaciji)






minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB

















minusY

minusX

+X


+X

+Y

minusY


Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Ia I Id DA


ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














ML M + L k1 kndash1



121-

1211

LL

LM L)(M L(M L)

kk

kk

dt

d

dt

d

5 6

Dagger




reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














reaktanta

11 LM L)(M L

kdt

d









EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















EP

M―X + Y

M―Y + X

X

M

Y

X

M

YX

M

Y

Dagger

Dagger

M―X + Y

M―Y + X

X

M

Y

X

M

Y

X

M

YX

M

Y

Dagger

Dagger



EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















EP

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

M―Y + X

X

M

Y

Dagger

X

M

Y

Dagger

M―X + Y

X

M

Y

X

M

Y





M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
















M―X + Y

X

M

Y M―Y + X

M―X + Y

X

M

Y

X

M

Y M―Y + X

EP




dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
















dostupnih orbitala


bipiramide

M

C1

C2 D

T

M

C1

C2 D

TE

E ndash DM

C1

C2 D

TE

M

C1

C2D

T

E

M

C1

C2

T

E








Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB



















Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Mehanizam izmjene







010

010031

L1

LM L)(M L

K

Kk

dt

d











ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB





















ndash


[Co(NH3)5N3]2+ + H2O


K0


ndash


[Co(NH3)5N3]2+ + H2O


K0K0


mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














mehanizama I




Ia Id





D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB

















D vs Id








Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















Zakon

brzinek1[ML]

I

K0[L1]0 lt 1

K0[L1]0 ~ 1 K0[L1]0 gt 1

Zakon


121

121

LL

LM L

kk

kk

010

01003

L1

LM L

K

Kk

L

LM L

1

121

k

kk










migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB


















migration)




L

CH3

L

C

L

L

L

CH3C O

CH3

O


Lrsquo Lrsquo

L

CH3

L

C

L

L

L

CH3C O

CH3

O



Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Umetanje karbonila

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CH3

CO

OC

OC

CO

CO

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


Mn

CH3

CO

OC

OC

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13ndash COndash CO

75

25


13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














13

Mn

CO

CO

OC

H3C

CO

CO

13

Mn

CO

CO

OC

H3C

CO

CO

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3


CO

CO

OC

OC

CH3

CO

ndash COndash COMn

CO

CO

OC

OC

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CH3

13

ndash COndash COMn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

Mn

CO

CO

OC

OC

CO

CO

CH3

13

50 (cis)

25

25 (trans)






ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB


















ML + L1 ML1 + L

















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
























metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















metanol


gdje je




00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













00001

0001

001

01

1

10

100

1000

10000

100000

1000000

0 2 4 6 8 10


nPt

CH3OH

Clminus

NH3

C5H5N NO2minus

C3H3N2

N3minusN2H4

Brminus

(CH3)2S

(Ph)3P

(Ph)3As

(NH2)2CS

Iminus

SeCNminus

CNminus

(Ph)3Sb

(CH3)2Se

SCNminus

SO32-



1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















1 Bazičnost


2 Polarizabilnost
























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB






























M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB






















M O

O

R

a

b



dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















dviju cis skupina





ndash gt







Trans-učinak















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB



























skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB





















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















skupinama
























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB

























Cis-učinak

Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













Utjecaj otapala

















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB






















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
















CrX2+ + H+ CrXH3+ K



2+ 3+

2+ 3+

obs


dk

dt

+

0 1

obs +

+ H=

1+ H

k k Kk

K













v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB





















v

2+ III

2+

1

Hg Co=

1+ Hg

a

K



K1

k2

k3



K1K1

k2

k3k3


Npr











M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB























M

O

O

H

O

O+ M

O

O

OH

O

M

O

O

OH

O

M

O

O

O

OH

M

O

O

O

OH

M

O

O

H

O

O +M

O

O

H

O

O +















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB



























protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB



















protona


2+ + Xndash k2


2+ brzo



III

III - III -1 2OH

-1 2

Co= = Co OH = Co OH

+

d nk kv k

dt k k










MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB






















MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














MOH2

OH2

+ L―L MOH2

L―L+ H2O

MOH2

L―LM

L

L+ H2O

M(L2)

[M(OH2)2]

k1 kndash1

k2 kndash2


ligandom

2

f 2 2 d 2

M (L )= M (O H ) L - L - M (L )

dk k

dt

1 2

f

-1 2

=+

k kk

k k ( )-1 -2

d

-1 2

=+

k kk

k k



H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB















H2N(CH2)2H2N

Pt

Cl

NH2(CH2)2NH2Cl

104 sndash1

H2N(CH2)2H2N

Pt

NH2

NH2Cl

073 sndash1

(CH2)2 Pt

NH2

NH2H2N

(CH2)2(H2C)2

H2N 2+2+2+2+

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2++

+ NH3

H3N

Pt

Cl

NH3Cl


H3N

Pt

NH3

NH2Cl

+ NH3 Pt

NH3

NH3H3N


2+2+++

+ NH3

k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













k2 ≫ kndash1




Primjer

Cr(H2O)63+ + H3N


3+H3N+CH2CO2



k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB













k2≪ kndash1







+





OH

Cr OH2

OH+

Cr OH2

O C O

CO

O

O

Cr

C

O

O

+

H3O+

O

Cr

C

O

O

+

+




O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
















O

O OH

Ni+

O

O O

H

Ni+

O

O ONi

O

O OH

ndash

+ Ni2+k1

kndash1

k1

kndash1

k2

kndash2

k2

kndash2

k3

kndash3

k3

kndash3

+ H+

6 7 8

1 2 3f

-1 -2 -1 3 -2 3

=+ +

k k kk

k k k k k k









HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB

















HL+ H+ + L K1





M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB














M

A

A

XM

AmdashA

X

H+

M

AmdashAH

X

Y

M

Y

X


potpuna zamjena


miješane specije

MA2 + NB2 MAB + NAB
























Documents

Pars secunda - unizg.hr · Pars secunda • Adicija, eliminacija, supstitucija • Pregradnja (izomerizacija) • Prijenos naboja (oksidacija i redukcija) ... interakcija je najučinkovitija