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    Lecture 3

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    Areeb Ahmad
    The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

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    Lecture 3

    Uploaded by

    Areeb Ahmad
    70 views23 pages
    The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

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    The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    70 views23 pages

    Lecture 3

    Uploaded by

    Areeb Ahmad
    The document discusses orbital degeneracy versus electronic degeneracy in transition metal complexes. It explains that complexes with distorted octahedral geometry form when ligands are of different kinds. The Jahn-Teller effect causes complexes to distort if their electronic ground state is degenerate in order to remove the degeneracy and lower energy. This effect is observed in d9 copper complexes but not d8 nickel complexes. Distortions are more pronounced when degeneracy occurs in eg orbitals and for d1 complexes compared to d9 complexes. Site preferences in spinel compounds are also discussed.

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    of 23

    Orbital Degeneracy versus Electronic Degeneracy

    Distortions in Octahedral Geometry


    L

    L L
    M
    L L

    L
    Regular Octahedron: Complexes with regular octahedral geometry are expected to 
    form, when all of the ligands are of the same kind

    Distorted Octahedron: Complexes with distorted octahedral geometry are expected to


    form, when the ligands are of different kinds
    Distortions in Octahedral Geometry
    If the ground electronic configuration of a non-linear complex is electronically
    degenerate, the complex will distort so as to remove the degeneracy and
    achieve a lower energy. This is called the Jahn-Teller Effect

    d8 d9

    eg eg

    t2g t2g

    Ni2+: Only one way of Cu2+: Two ways of filling the eg orbitals;
    filling the orbitals; not there is degeneracy and Jahn-Teller
    degenerate and no Jahn- Distortion is observed
    Teller Distortion
    Distortions in Octahedral Geometry
    Jahn-Teller Distortion in Cu(II) Complexes

    dx2-y2

    eg
    energy
    dz2

    dxy
    t2g

    Cu(II) in regular octa- dxz dyz


    hedral environment [CuF6]4-
    Cu(II) after J-T distortion
    Jahn-Teller Distortion in d9 Complexes

    Δo >> δ1 > δ2.
    Jahn-Teller Distortion in d1 Complexes

    dz2
    eg
    energy
    dx2-y2

    dxz dyz
    t2g

    d1 in regular octa- dxy


    hedral environment
    d1 after J-T distortion
    d1 Vs d9

    d9 d1

    Distortions are more pronounced if the degeneracy occurs in an eg orbital
    Distortions in Low-Spin Complexes

      


    Distortions in High-Spin Complexes

     

     
    Site Preference in Spinels
    Spinel – MgIIAlIII2O4
    AIIBIII2O4

    The oxide ions form a close packed arrangement with octahedral and tetrahedral voids
    and the metal ions occupy the voids.

    Normal Spinels: (AII)tet(BIII2)octO4


    The divalent AII ions occupy the tetrahedral voids, whereas the trivalent BIII ions
    occupy the octahedral voids in a close packed arrangement of oxide ions.
    MgAl2O4, Mn3O4, ZnFe2O4, FeCr2O4

    Inverse Spinels: (BIII)tet(AIIBIII)octO4


    The AII ions occupy the octahedral voids, whereas half of BIII ions occupy the
    tetrahedral voids.
    Fe3O4, CoFe2O4, NiFe2O4
    Site Preference in Spinels

    NiFe2O4

    Ni is in +2 oxidation state and has 8 electrons in the d orbitals


    In a tetrahedral void,
    Configuration – e4t24; CFSE – 0.8 Δt (0.4 Δo)
    In an octahedral void,
    Configuration – t2g6eg2; CFSE – 1.2 Δo
    Fe is in +3 oxidation state and has 5 electrons in the d orbitals
    In a tetrahedral void,
    Configuration – e2t23; CFSE – 0
    In an octahedral void,
    Configuration – t2g3eg2; CFSE – 0

    Hence, it is advantageous to have Ni2+ ion in the octahedral voids. This results in an
    inverse spinel structure for the compound.
    FeIII[NiIIFeIII]O4
    Site Preference in Spinels

    Mn3O4

    When Mn is in +2 oxidation state, it has 5 electrons in the d orbitals


    In a tetrahedral void,
    Configuration – e2t23; CFSE – 0
    In an octahedral void,
    Configuration – t2g3eg2; CFSE – 0
    When Mn is in +3 oxidation state, it has 4 electrons in the d orbitals
    In a tetrahedral void,
    Configuration – e2t22; CFSE – 0.4 Δt (0.2 Δo)
    In an octahedral void,
    Configuration – t2g3eg1; CFSE – 0.6 Δo

    Hence, it is advantageous to have Mn3+ ions in the octahedral voids. This results in a
    normal spinel structure for the compound.
    MnII[MnIII]2O4
    Origin of Color

    The Beer-Lambert Law


    A = log10(Io/I) = εcl
    where ε is the molar extinction coefficient ( in L cm-1 mole-1 ), c is concentration in mole L-1
    and l is the path length in cm. A is known as ‘Absorbance’ and it is dimensionless.
    Color of [Ti(H2O)6]3+

    Absorption at 520 nm
    gives the complex its
    purple color

    A more resolved absorption spectrum of the complex has a shoulder


    Color and CFT
    Color and CFT

    [Cr(NH3)6]3+ [Cr(NH3)5Cl]2+

    Strong ligands, leading to Relatively weak set of ligands,


    high Δo. Absorbs violet leading to reduced Δo. Absorbs
    and appears yellow. yellow and appears magenta.
    Laporte Rule

    In a molecule or ion possessing center of symmetry, transitions are not allowed


    between orbitals of same parity. Transitions are only possible between orbitals that
    differ by Δl = ±1; ‘l’ is the orbital quantum number.

    Examples of forbidden transitions are: s to s, d to d, p to f etc.

    Tetrahedral geometry is not affected by this rule as it does not have a center of
    symmetry.
    As a consequence, ε for tetrahedral complexes are 100 times more than the ε for
    octahedral complexes.

    Even octahedral complexes lose their center of symmetry transiently due to


    unsymmetrical vibrations. This leads to color in octahedral and square planar
    complexes

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