Inorganic Chemistry 2 - Yazdchem.yazd.ac.ir/gorji/Lecture/Adv Inorganic Chemistry/Adv Inorganic...

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Advanced Inorganic Chemistry

Alireza Gorjiagorji@yazd.ac.ir

Department of Chemistry, Yazd University

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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

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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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[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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- Electronic effect

- Steric effect

- Solvent effect

- Lattice effect

- Counter ion effect

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Polymerization Isomerism ایزومری پلیمری

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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

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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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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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تحمیل ایزومری به وسیله لیگاند

fac فقط mer فقط 17agorji@yazd.ac.ir

2- StereoisomerismStereoisomerism استریوایزومری

2- Optical isomerism نوری ایزومری

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Sn S1= S2=i

Cn Dn

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Chiral Complexes

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Cn Dn

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Cn Dn

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Presentation of [M(en)3]

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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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optically inactive, nL= nR

Plane Polarized Light

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Plane Polarized Light

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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.

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• Positive Cotton effect

• Negative Cotton effect

The Cotton Effect in ORD

Circular Dichroism

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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

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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

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][2][

2

CD is more commonly used than ORD

to study molecules.

- Better resolution

- Better sensitivity.

- Easier to assign41agorji@yazd.ac.ir

ORD, CD and UV of Camphor

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CD Instrumentation

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The Cotton Effect

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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

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1- Determination of absolute configuration (&)

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1- Determination of absolute configuration (&)

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2- Assignment of Electronic spectra

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