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    Topic 10 Isomerism

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    izz isalah
    There are two main types of isomerism in coordination compounds: structural isomers and stereoisomers. Structural isomers have the same molecular formula but different connectivity of atoms, while stereoisomers have the same connectivity but different spatial arrangements. Some examples of structural isomers are coordination-sphere isomers and ionization isomers. Stereoisomers include geometric isomers (cis/trans and facial/meridional), optical isomers (enantiomers), and hydrate isomers which differ in their number of water ligands. Coordination compounds find many uses including as dyes, pigments, in analytical chemistry as indicators or masking agents, and in industrial and biological applications.

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    Topic 10 Isomerism

    Uploaded by

    izz isalah
    69 views41 pages
    There are two main types of isomerism in coordination compounds: structural isomers and stereoisomers. Structural isomers have the same molecular formula but different connectivity of atoms, while stereoisomers have the same connectivity but different spatial arrangements. Some examples of structural isomers are coordination-sphere isomers and ionization isomers. Stereoisomers include geometric isomers (cis/trans and facial/meridional), optical isomers (enantiomers), and hydrate isomers which differ in their number of water ligands. Coordination compounds find many uses including as dyes, pigments, in analytical chemistry as indicators or masking agents, and in industrial and biological applications.

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    There are two main types of isomerism in coordination compounds: structural isomers and stereoisomers. Structural isomers have the same molecular formula but different connectivity of atoms, while stereoisomers have the same connectivity but different spatial arrangements. Some examples of structural isomers are coordination-sphere isomers and ionization isomers. Stereoisomers include geometric isomers (cis/trans and facial/meridional), optical isomers (enantiomers), and hydrate isomers which differ in their number of water ligands. Coordination compounds find many uses including as dyes, pigments, in analytical chemistry as indicators or masking agents, and in industrial and biological applications.

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    © All Rights Reserved
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    Download as pptx, pdf, or txt
    69 views41 pages

    Topic 10 Isomerism

    Uploaded by

    izz isalah
    There are two main types of isomerism in coordination compounds: structural isomers and stereoisomers. Structural isomers have the same molecular formula but different connectivity of atoms, while stereoisomers have the same connectivity but different spatial arrangements. Some examples of structural isomers are coordination-sphere isomers and ionization isomers. Stereoisomers include geometric isomers (cis/trans and facial/meridional), optical isomers (enantiomers), and hydrate isomers which differ in their number of water ligands. Coordination compounds find many uses including as dyes, pigments, in analytical chemistry as indicators or masking agents, and in industrial and biological applications.

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    Isomerism in Coordination

    Compounds
     Isomers
    Compounds with the same molecular
    formula but different arrangement of
    atoms in space

    Major Types
    1. Structural isomers
    2. Stereoisomers
     
    Isomerism
    Structural Isomers
    Compound with different atomic bond
    connectivity.

    Stereoisomers
    Same atomic connectivity but different
    arrangement.
    Structural Isomers
    Coordination-sphere isomers
    ◦ In this case compound is made up of cation and
    anion and the isomerism arises due to interchange of
    ligands between complex cation and complex anion

    Example:
    [Co(NH3)6][Cr(CN)6] vs   [Cr(NH3)6][Co(CN)6]
    hexaaminecobalt(III) hexacyanochromate(III) 
    hexaaminechromium(III) hexacyanocobaltate(III)
    Ionization Isomers
     Interchange of an ionic ligand with first coordination
    sphere with an anion outside coordination sphere

     Example: [Co(NH3)5Br]SO4
    [Co(NH3)5SO4]Br

    [PtCl2(NH3)4]Br2
    [PtBr2(NH3)4]Cl2
    Ionization Isomers
    Example 1
    [Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl

    Consider ionization in water


    [Co(NH3)5Cl]Br  [Co(NH3)5Cl]+ + Br-

    [Co(NH3)5Br]Cl  [Co(NH3)5Br]+ + Cl-


    Ionization Isomers
    Example 2
    [Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl

    Consider precipitation
    [Co(NH3)5Cl]Br(aq) + AgNO3(aq)  [Co(NH3)5Cl]NO3(aq) + AgBr(s)

    [Co(NH3)5Br]Cl(aq) + AgNO3(aq)  [Co(NH3)5Br]NO3(aq) + AgCl(aq)


    Hydrate Isomers
    Hydrate isomers have the same composition but differ
    In the number of water molecules present as ligands
    And the phenomenon is called hydrate isomerism.

    Examples : [Cr(H2O)6]Cl3 
                        [Cr(H2O)5Cl]Cl2.H2O 
    pentaaquachlorochromium (III) chloride monohydrate
                      [Cr(H2O)4Cl2]Cl.2H2O 
    tetraaquadichloro chromium (III) chloride dihydrate
    Hydrate Isomers

    i) six H2O in coordination sphere -Violet


    ii) five H2O and one Cl in coordination sphere - Dark Green
    iii) four H2O and two Cl in coordination sphere - Green
    Linkage isomers
    ◦ difference in the atom of a ligand bonded to
    the metal in the complex

    Example

    ◦ [Co(NH3)5(ONO)]2+ vs. [Co(NH3)5(NO2)]2+

    ◦ [Co(NH3)5(SCN)]2+ vs. [Co(NH3)5(NCS)]2+

     Co-SCN vs. Co-NCS


    Linkage isomers

    Nitro ligand as an N-donor

    Nitrito ligand as an O-donor


    Linkage isomers

    2,2’’-bipyridine -bipyridine

    Two compounds formed by the linkage isomer of bpy is


    shown. Small changes in ligand bonding could result in
    dramatic chemical property change
    Stereoisomers
    Geometric isomers
    Square Planar:
     Compound type       No. of isomers

    Ma2b2                     (cis- and trans-)

    Octahedral:
     Compound type No. of isomers
    Ma4b2 (cis- and trans-)
    Ma3b3 (fac- and mer-)
    MAA2b2 (cis- and trans-)
    Geometrical isomer
    ◦ cis- isomers: have identical groups of atoms
    (ligands) are adjacent to each other in structural
    formula.

    ◦ trans- isomers: have identical groups of atoms


    (ligands) opposite sides from each other in structural
    formula.

    ◦ meridinal isomers (mer-): placing 3 identical ligands


    in a plane bisecting the molecule of the octahedral

    ◦ facial isomers (fac-): placing 3 ligands on one


    triangular face of the octahedral
    FOUR-COORDINATE COMPLEX –
    square planar
    Geometric Isomers of Pt(NH3)2Cl2: In the cis
    isomer, atoms are on the same side. In the trans
    isomer, atoms are on opposite sides.
    SIX-COORDINATE COMPLEX -
    octahedral
    Geometric Isomers of [Co(NH3)4Cl2]Cl:
    SIX-COORDINATE COMPLEX -
    octahedral
     Complexes of formula ML3L’3 may have 2 isomeric
    formed called fac- and mer- Cl
     L and L’ :monodentate ligand

    H3N
    Cl Cl
    Co
    H3N
    H3N Cl Cl

    Co
    H3N Cl Cl
    NH3

    NH3
    N
    fac-[Co(NH3)3Cl3] Cl
    Co
    N
    Cl

    N
    N

    N N
    N
    Co
    N N N
    N
    Co
    N N N

    N N

    fac-[Co(dien)2]3+

    N
    N
    Co
    N
    N

    N
    SIX-COORDINATE COMPLEX -
    octahedral

    NH3 NH3

    H3N Cl
    Co H3N
    Cl
    Cl Cl Cl
    Co
    Cl
    NH3
    mer-[Co(NH3)3Cl3] NH3
    N N

    N N N
    Co Co
    N

    N N N
    N

    N
    N
    mer-[Co(dien)2]3+
    left is mer[Co(NH3)3(H2O)3]2+ right is fac[Co(NH3)3(H2O)3]2+
    Geometric isomers

    diaminebischloroplatinum(II)
    Geometric isomers

    Cis trans
    Geometric isomers

    cis isomer trans isomer


    Pt(NH3)2Cl2
    Geometric isomers

    cis isomer trans isomer


    [Co(H2O)4Cl2]+
    Stereoisomers
    Optical isomers
     Isomer complex in which the atomic connection
    are the same but arrangement is such that the
    two complexes are not superimposable.
    Optical isomer
     Enantiomers have:
    SAME : melting points, boiling points, dipole moments, solvent
    capabilities

    DIFFERENT : ability to rotate the plane of polarized light in


    opposite directions

     Polarimeter : to measure the rotation of polarized light by


    optical isomers
     Plane-polarized light is obtained by passing ordinary light
    through a polarizing filter.
    Example 1

     Stereoisomers- optical isomers or enantiomers, are mirror


    images of each other.
     Just as a right hand will not fit into a left glove, two
    enantiomers cannot be superimposed on each other.
    A molecule or ion that exists as a pair of enantiomers
    is said to be chiral.
    Example 2

    mirror plane

    cis-[Co(en)2Cl2]+
    Example 2 rotate mirror image 180°

    180 °
    Example 2
    nonsuperimposable

    cis-[Co(en)2Cl2]+
    Example 2
    enantiomers

    cis-[Co(en)2Cl2]+
    Example 3

    mirror plane

    trans-[Co(en)2Cl2]+
    Example 3 rotate mirror image 180°

    180 °

    trans-[Co(en)2Cl2]+
    Example 3
    Superimposable-not enantiomers

    trans-[Co(en)2Cl2]+
    Properties of Optical Isomers

    Enantiomers
    ◦possess many identical properties
    (solubility, melting point, boiling
    point, color, chemical reactivity)
    A molecule or ion that exists as a pair of enantiomers
    is said to be chiral.
    Uses of Coordination Compounds
    Dyes and Pigments: Coordination compounds have been used from the earliest
    times as dyes and pigments, for example madder dye which is red, was used by
    the ancient Greeks and others. It is a complex of Hydroxyanthraquinone. A more
    modern example is the pigment copper phthalocyanine, which is blue.

    Analytical Chemistry: You have already encountered many such uses during the
    laboratory course.
    (a) Colour Tests: Since many complexes are highly coloured they can be used as
    colourimetric reagents e.g. formation of red 2,2'-bipyridyl and l,l0-phenanthroline
    complexes as a test for Fe(II)
    (b) Gravimetric Analysis: Here chelating ligands are often used to form insoluble
    complexes e.g. Ni(DMG)2 and Al(oxine)3 (see laboratory manual).
    (c) Complexometric Titrations and Masking Agents: An example of this is the use of
    EDTA in the volumetric determination of a wide variety of metal ions in solution, e.g.
    Zn2+, Pb2+, Ca2+,Co2+, Ni2+, Cu2+, etc. By careful adjustment of the pH and using
    suitable indicators, mixtures of metals can be analysed, e.g. Bi3+ in the presence of
    Pb2+ (see laboratory manual). Alternatively, EDTA may be used as a masking agent
    to remove a metal ion which would interfere with the analysis of a second metal ion
    present.
    Sequestering Agents: Related to their use as masking agents is the use of
    ligands for "sequestering" i.e. for the effective removal of objectionable ions from
    solution in industrial processing, e.g. EDTA is used to "soften" water. The addition
    of EDTA to water is used in boilers etc., to prevent "scaling" or build up of insoluble
    calcium salts.

    Extraction of Metals: Sometimes certain metals can be leached from their ores
    by formation of stable complexes e.g. Ag and Au as complexes of cyanide ion.

    Bio-Inorganic Chemistry: Naturally occurring complexes include haemoglobin,


    chlorophyll, vitamin B12 etc.
    EDTA and other complexing agents have been used to speed the elimination of
    harmful radioactive and other toxic elements from the body. (e.g. Pb2+). In these
    cases soluble metal chelate complexes are formed.

    Chemo-therapy: an example here is the use of cis-PtCl2(NH3)2 as an anti-tumour


    drug.

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