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1 Advanced Inorganic Chemistry Alireza Gorji [email protected] Department of Chemistry, Yazd University Isomers (same formula but different properties) Stereoisomers (same bonds, different spatial arrangements) Structural isomers (different bonds) Optical isomerism Geometric (cis-trans) isomerism Linkage isomerism Coordination isomerism Isomerism زومری ای[email protected] 2

Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji [email protected] Department

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Page 1: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

1

Advanced Inorganic Chemistry

Alireza [email protected]

Department of Chemistry, Yazd University

20_441

Isomers

(same formula but different properties)

Stereoisomers

(same bonds, different

spatial arrangements)

Structural

isomers

(different bonds)

Optical

isomerism

Geometric

(cis-trans)

isomerism

Linkage

isomerism

Coordination

isomerism

Isomerism ایزومری

[email protected] 2

Page 2: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

2

Ionization Isomerism ایزومری یونش

[CrSO4(NH3)5]Cl

[CrCl(NH3)5]SO4

pentaaminsulfatochromium(III) chloride

pentaaminchlorochromium(III) sulfate

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Hydrated Isomerism ایزومری آب پوشی

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Page 3: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[Co(NH3)4(NO2)Cl]Cl & [Co(NH3)4(ONO)Cl]Cl

[Co(SCN)(NH3)5]+ & [Co(NCS)(NH3)5]

+

Ambidentate Ligands لیگاندهای دوسردندانه

NCS- NO2- R-CONH2

Linkage Isomerism ایزومری اتصال

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[Co(NH3)5(NO2)]Cl2Pentaamminenitrocobalt(III) chloride

[Co(NH3)5(ONO)]Cl2Pentaamminenitritocobalt(III) chloride

Linkage Isomerism ایزومری اتصال

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Page 4: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected] 7

- Electronic effect

- Steric effect

- Solvent effect

- Lattice effect

- Counter ion effect

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Page 5: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected] 9

[email protected] 10

Page 6: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected] 11

[email protected] 12

Polymerization Isomerism ایزومری پلیمری

Page 7: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

7

20_441

Isomers

(same formula but different properties)

Stereoisomers

(same bonds, different

spatial arrangements)

Structural

isomers

(different bonds)

Optical

isomerism

Geometric

(cis-trans)

isomerism

Linkage

isomerism

Coordination

isomerism

Isomerism ایزومری

[email protected] 13

Stereoisomerism استریوایزومری1- Geometric isomerism

1. Geometric isomerism (cis-trans):

Pt(NH3)2Cl2

2. Geometric isomerism (fac-mer):

IrH3(PR3)3

• Atoms or groups arranged differently spatially relative to metal ion

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Page 8: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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Geometric Isomerism ایزومری هندسی

cis-trans ترانس–سیس

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ML3X3•fac (facial) وجهی

three identical ligands occupying the

corners of a common triangular

•mer (meridional) کمربندی

three identical ligands occupying three

consecutive corners of a square plane

Geometric Isomerism ایزومری هندسی

fac-mer کمربندی –وجهی

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Page 9: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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تحمیل ایزومری به وسیله لیگاند

fac فقط mer فقط [email protected]

2- StereoisomerismStereoisomerism استریوایزومری

2- Optical isomerism نوری ایزومری

18

Sn S1= S2=i

Cn Dn

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Chiral Complexes

Page 10: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected] 19

Cn Dn

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Cn Dn

Page 11: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected] 21

[email protected] 22

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[email protected] 23

[email protected] 24

Page 13: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected] 25

[email protected] 26

Page 14: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected]

[email protected] 28

Page 15: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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Presentation of [M(en)3]

[email protected] 29

[email protected] 30

Page 16: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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Chiroptic Techniques

•Plane and circularly polarized light

•Definitions of terms

•Optical rotary dispersion (ORD)

•Circular dichroism (CD)

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Types of polarized light

• Plane polarized light consists two circularly polarized components of equal intensity

• Two circularly polarized components are like left-and right-handed springs

• As observed by looking at the source, right-handed circularly polarized light rotates clockwise

• Frequency of rotation is related to the frequency of the light

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Page 17: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected] 33

optically inactive, nL= nR

Plane Polarized Light

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Plane Polarized Light

Page 18: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected] 35

Optical Rotation

optically inactive, nL= nR

optically active, nL nR

n=c/cv

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Optical Rotatory Dispersion (ORD)

moleper gramsin MW theis where,)cm M (deg ][][ rotation Molar

(g/mL)ion concentrat theis and (cm)length path theis where, rotation Specific

line) D Na the589;(normally •

180rotation of angle observed The

1-1-

RL

Mdc

MM

cddc

nnd

The technique of optical rotatory dispersion (ORD)

examines the wavelength dependence of optical activity.

Page 19: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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• Positive Cotton effect

• Negative Cotton effect

The Cotton Effect in ORD

Circular Dichroism

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Page 20: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected]

Circular Dichroism

• is therefore the angle between the initial plane of polarization and the major axis of the ellipse of the resultant transmitted light

• A quantity is defined such that tan is the ratio of the major and minor axis of the ellipse of the transmitted light

• ’ approximates the ellipticity

• When expressed in degrees, ’ can be converted to a specific ellipticity [] or a molar ellipticity []

• CD is usually plotted as []

θ100.3032εε

10θ y ellipticitmolar

dc' y ellipticit specific

3

rl

2

M

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Circular Dichroism

Page 21: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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)(3300

).( y"ellipticit" as CD express sinstrument commercial reasons, historicalFor

)()()(

RLCD

Optical rotatory dispersion (ORD) and circular dichroism (CD) are mathematically

related. If you measure one, you can calculate the other by means of functions called

Kronig-Kramers Transforms.

dM

dM

o

o

o

o

o

o

22

22

][2][

2

CD is more commonly used than ORD

to study molecules.

- Better resolution

- Better sensitivity.

- Easier to [email protected]

ORD, CD and UV of Camphor

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Page 22: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected]

CD Instrumentation

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The Cotton Effect

Page 23: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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Use of CD and ORD spectra

1- Determination of absolute configuration (&)

2- Assignment of Electronic spectra

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1- Determination of absolute configuration (&)

Reference:d6 low spin

Page 24: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

12/4/2015

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[email protected]

1- Determination of absolute configuration (&)

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Page 25: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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1- Determination of absolute configuration (&)

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2- Assignment of Electronic spectra

Page 26: Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic Chemistry 11.pdfAdvanced Inorganic Chemistry Alireza Gorji agorji@yazd.ac.ir Department

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[email protected] 51

[email protected] 52

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[email protected] 53

[email protected] 54

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[email protected] 55

[email protected] 56

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[email protected] 57