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    The document discusses molecular orbital theory and its application to coordination compounds and transition metal complexes. It introduces linear combination of atomic orbitals (LCAO) approach to construct molecular orbitals and the role of symmetry in determining orbital interactions. It then discusses how molecular orbitals are used to explain electronic spectra, magnetism and other properties of complexes. Examples of sigma and pi bonding in octahedral, tetrahedral and square planar complexes are presented along with their molecular orbital diagrams. Evidence of pi bonding from metal carbonyls is also discussed.

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    The document discusses molecular orbital theory and its application to coordination compounds and transition metal complexes. It introduces linear combination of atomic orbitals (LCAO) approach to construct molecular orbitals and the role of symmetry in determining orbital interactions. It then discusses how molecular orbitals are used to explain electronic spectra, magnetism and other properties of complexes. Examples of sigma and pi bonding in octahedral, tetrahedral and square planar complexes are presented along with their molecular orbital diagrams. Evidence of pi bonding from metal carbonyls is also discussed.

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    The document discusses molecular orbital theory and its application to coordination compounds and transition metal complexes. It introduces linear combination of atomic orbitals (LCAO) approach to construct molecular orbitals and the role of symmetry in determining orbital interactions. It then discusses how molecular orbitals are used to explain electronic spectra, magnetism and other properties of complexes. Examples of sigma and pi bonding in octahedral, tetrahedral and square planar complexes are presented along with their molecular orbital diagrams. Evidence of pi bonding from metal carbonyls is also discussed.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    602 views36 pages

    MOT Upload

    Uploaded by

    Sarthak Singh
    The document discusses molecular orbital theory and its application to coordination compounds and transition metal complexes. It introduces linear combination of atomic orbitals (LCAO) approach to construct molecular orbitals and the role of symmetry in determining orbital interactions. It then discusses how molecular orbitals are used to explain electronic spectra, magnetism and other properties of complexes. Examples of sigma and pi bonding in octahedral, tetrahedral and square planar complexes are presented along with their molecular orbital diagrams. Evidence of pi bonding from metal carbonyls is also discussed.

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    of 36

    Molecular Orbital Theory of

    Coordination Compounds

    - Huheey, Keiter & Keiter, Inorganic Chemistry, 4th Edn


    - F.A. Cotton, Chemical Application of Group Theory

    Crystal Field Theory

    Explain reasonably the electronic spectra and magnetism of TM complexes.

    The interaction b/w metal and ligand is purely electrostatic (no covalency!)

    Evidences for covalent character:

    Nephelauxetic effect:

    e-e repulsion in complexes is somewhat


    less than that in a free ion

    Electron paramagnetic resonance (EPR)


    spectroscopy: hyperfine splitting pattern

    Molecular Orbital Theory


    In Molecular Orbital Theory:
    Orbital structure of molecules Shapes & energy order of MOs.

    Linear Combination of Atomic Orbitals (LCAO):

    c
    i i
    i

    Shape of MOs are determined by the cs (both magnitude & sign).


    (e.g. Variation Theorem Solve Secular equations)
    N
    ( H jk i S jk ) cki 0,
    k 1

    j 1,2, , N

    Electronic structures are obtained by placing electrons in the MOs


    (starting with the lowest one).
    Construction of MOs: Decompose the system into two or more simple
    subsystem whose orbitals (atomic or molecular) are known. Then allow
    the orbital of the fragments to interact (LCAO).
    Interaction between two orbitals:
    Role of symmetry:

    Interactions between two orbitals


    Same type

    Different types

    ,1
    1

    1 2

    2(1 S12 )

    ; E H11

    S2
    E E

    E E S 1* 2 d

    , 2
    2

    H12 H11S12
    1 S12

    In order to have non-zero S, orbitals must be bases for the same irreducible
    representation of the molecular symmetry group, i.e. they must have same
    symmetry, ONLY ORBITALS OF SAME SYMMETRY INTERACT.

    MO Theory of Transition metal complexes

    s, p electrons: minimum 24 orbitals


    Results with NN Secular matrix;
    N = 33 (minimum)

    nd, (n+1)s, (n+1)p : minimum 9 orbitals

    l l m m p p

    Role of Symmetry in Bonding


    e.g. Water:

    Participating orbitals: O: 2s, 2p; H: 1s


    6 6 Secular matrix

    To construct the MOs for an AXn molecule, we need to combine the atomic orbitals on X
    and then match the resultant combinations with the atomic orbitals of the central atom A.
    With Group Theory, we can derive the linear combinations systematically.

    1. Determine the symmetries of participating orbitals:

    A1 : s, pz ; B1 : px ; B2 : p y

    2. Determine the characters of representation:

    Reduction Formula:

    1
    ai ( Rk ) ( R )n( R )
    i k
    k
    hk

    Symmetry Adopted Linear Combination


    3. Determine the linear combination with appropriate symmetry:

    (ii) By Inspection

    (i) Projection Operator:


    P [ (R )R ]
    i k k
    k

    SUMMARY

    Symmetry

    Orbitals on O

    Orbitals on H

    MO

    A1

    2s, 2Pz

    1sa+1sb

    1a1, 2a1, 3a1

    B2

    2Py

    1b2

    B1

    2Px

    1sa-1sb

    1b1, 2b1

    Formation of MOs in H2O


    Sym
    metry

    Orbitals
    on O

    Orbitals
    on H

    MO

    A1

    2s, 2Pz

    1sa+1sb

    1a1, 2a1, 3a1

    2py, b2

    2pz, a1
    B2

    2Py

    1b2

    B1

    2Px

    1sa-1sb

    1b1, 2b1
    2px, b1

    2s, a1

    MO Diagram for H2O

    2p

    1sa - 1sb
    1sa + 1sb

    2s

    MOTof Transition metal complexes


    L
    I
    G
    A
    N
    D
    S

    Metal

    Variation principle:

    N
    ( F jk i S jk ) aki 0,
    k 1

    j 1,2, , N

    Octahedral ML6 Sigma Bonding

    (s; p , p , p ; d
    ,d )
    x y z x2 y 2 z 2

    P [ (R )R ]
    A. Finding SALC by Projection Operator Method:
    i k k
    k
    a
    P 1 (L ) ~ 4(L L L L L L )
    1
    1 2 3 4 5 6

    Determination of SALCs
    a 1 (L L L L L L )
    6 1

    1g

    a1g

    e(1) 1 (2L 2L L L L L )
    g

    12

    t(1) 1 (L L )
    1u

    2 1

    e(2) 1 (L L L L )

    t(2) 1 (L L )
    1u

    2 3

    4 3

    t(3) 1 (L L )
    1u

    2 5

    eg

    t1u

    A -bond MO Diagram of Octahedral ML6

    Example:
    [Co(NH3)6]3+
    18e: diamagnetic

    [CoF6]318e: paramagnetic ??

    Tetrahedral ML4 Sigma Bonding

    Tetrahedral ML4 Sigma Bonding: MOs

    [CoCl4]215e: paramagnetic

    Sq. Planar ML4 Sigma Bonding

    Sq. Planar ML4 Sigma Bonding: MOs

    Typical for d8 ion:


    16e: diamagnetic

    Octahedral ML6 Pi- Bonding

    Octahedral ML6 Pi- Bonding

    Metal Complexes with Ligands containing orbitals

    Octahedral ML6 Pi- Bonding: SALCs

    t2g

    Effect of Pi-bonding in MOs

    Additional t2g

    Example: [CoF6]3LGOs constructed


    from 2p (F) orbitals

    Pi- Bonding & MO Theory

    MO diagram for Pi-donor ligands

    MO diagram for Pi-acceptor ligands

    Importance of - Bonding:
    Explaining the Spectrochemical Series
    Determining patterns in ligand substitution reaction
    Reactivity & stability of organometallics

    Evidences for Pi Bonding: Metal Carbonyls


    Bonding Model: -donor (OC M) and a -acceptor (OC M)

    Crystallography:
    Greater -bonding
    longer C O bond,
    shorter M C bond
    Longer C O bond than the normal CO in
    free CO (112.8 pm) could be taken as
    evidence for bonding. However, M C
    bond length gives better indication!

    Example: Re(CH3)(CO)5

    Re CO length: 200.4 pm (24 pm shorter than corresponding


    -only bond.

    Evidences for Pi Bonding: Metal Carbonyls


    Phosphine & Phosphite Derivatives of Cr(CO)6

    Evidences for Pi Bonding: Metal Carbonyls


    IR Spectroscopy: (CO stretching frequency very useful)
    HOMO (3) LUMO (2) causes the C O stretching frequency to drop from
    2143 to 1489 cm-1.

    Favored by system with


    positive charge
    accumulated on M

    Favored by system with


    negative charge which
    enhances back
    donation.

    So, net charge on carbonyl compounds have a


    profound effect on CO stretching frequency.

    Greater -ve charge on M Stronger -Bonding Weaker C O bond


    Lower IR frequency

    Photoelectron Spectroscopy: Cr(CO)6


    Removal of electron from t2g orbital should weaken
    the M C bond and decrease MC

    MC for Cr(CO)6 ion is 325 cm-1 (379 cm-1 for


    neutral) corresponds to 14 pm increase in M C
    length on ionization

    MO Theory of Metallocenes
    Chapter 15: Huhee
    Chapter 7: Cotton

    Sandwich Compounds: Metallocenes


    Complexes in which a metal atom is found between two parallel carbocyclic rings:
    Sandwich compounds. Metal-ligand bond b/w a metal & the orbitals of C5H5.

    Metallocenes & 18-electron rule: usually do not obey

    SALCs of ferrocenes

    Molecular Orbitals of Cp-

    Molecular Orbitals of Cp-

    a1

    e1

    e2

    Molecular Orbitals of cycloalkenes

    SALCs of [CpCp]2-

    Molecular Orbitals of ferrocenes

    Molecular Orbital diagram of metallocenes

    Structures of Cyclopentadienyl Compounds

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