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  • 12/4/2015

    1

    Advanced Inorganic Chemistry

    Alireza Gorji agorji@yazd.ac.ir

    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

    agorji@yazd.ac.ir 2

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    Ionization Isomerism ایزومری یونش

    [CrSO4(NH3)5]Cl

    [CrCl(NH3)5]SO4

    pentaaminsulfatochromium(III) chloride

    pentaaminchlorochromium(III) sulfate

    agorji@yazd.ac.ir 3

    Hydrated Isomerism ایزومری آب پوشی

    agorji@yazd.ac.ir 4

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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

    agorji@yazd.ac.ir 5

    [Co(NH3)5(NO2)]Cl2 Pentaamminenitrocobalt(III) chloride

    [Co(NH3)5(ONO)]Cl2 Pentaamminenitritocobalt(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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    agorji@yazd.ac.ir 11

    agorji@yazd.ac.ir 12

    Polymerization Isomerism ایزومری پلیمری

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    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

    agorji@yazd.ac.ir 13

    Stereoisomerism استریوایزومری 1- 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

    agorji@yazd.ac.ir 14

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    Geometric Isomerism ایزومری هندسی

    cis-trans ترانس–سیس

    15agorji@yazd.ac.ir

    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

    agorji@yazd.ac.ir 16

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    تحمیل ایزومری به وسیله لیگاند

    fac فقط mer فقط 17agorji@yazd.ac.ir

    2- Stereoisomerism Stereoisomerism استریوایزومری

    2- Optical isomerism نوری ایزومری

    18

    Sn S1= S2=i

    Cn Dn

    agorji@yazd.ac.ir

    Chiral Complexes

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    Cn Dn

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    Cn Dn

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    27agorji@yazd.ac.ir

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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)

    31agorji@yazd.ac.ir

    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

    32agorji@yazd.ac.ir

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    agorji@yazd.ac.ir 33

    optically inactive, nL= nR

    Plane Polarized Light

    agorji@yazd.ac.ir 34

    Plane Polarized Light

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    agorji@yazd.ac.ir 35

    Optical Rotation

    optically inactive, nL= nR

    optically active, nL nR

    n=c/cv

    agorji@yazd.ac.ir 36

    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 •

    180 rotation of angle observed The

    1-1-

    RL

    M dc

    M M

    cd dc

    nn d

     

     

     

     

    

    

    

    The technique of optical rotatory dispersion (ORD)

    examines the wavelength dependence of optical activity.

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    agorji@yazd.ac.ir 37

    • Positive Cotton effect

    • Negative Cotton effect

    The Cotton Effect in ORD

    Circular Dichroism

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    39agorji@yazd.ac.ir

    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

    40agorji@yazd.ac.ir

    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.

       

     

     

     

     

     

    

     

     

    d M

    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 assign 41agorji@yazd.ac.ir

    ORD, CD and UV of Camphor

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    43agorji@yazd.ac.ir

    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

    agorji@yazd.ac.ir 46

    1- Determination of absolute configuration (&)

    Reference: d6 low spin

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    47 agorji@yazd.ac.ir

    1- Determination of absolute configuration (&)

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    49agorji@yazd.ac.ir

    1- Determination of absolute configuration (&)

    50 agorji@yazd.ac.ir

    2- Assignment of Electronic spectra

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