Transition metal complex bonding and spectroscopy review
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Transition Metal Complex Bonding and Spectroscopy Review

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Transition metal complex bonding and spectroscopy review

Transition Metal ComplexBonding and SpectroscopyReview


Transition metal complex bonding and spectroscopy review

Bonding:Donor-Acceptor Interactions Roles of metal and ligands Making MO Diagrams for Complexes Counting d-electrons Filling in the MO Diagram High spin/Low spin cases Comparing structures for bond strength


Donor acceptor mo interactions

Donor Acceptor MO Interactions


Roles metal d orbitals acceptors ligands donors mo diagram in general

Roles: Metal d-orbitals = acceptors Ligands = donorsMO Diagram in general:


Specific interactions for each d orbital based on ligand position

Specific Interactions for each d orbital based on ligand position

Use Angular Overlap parameters:

--for each d-orbital, add up the interactions for all the ligands

-- the total for that orbital determines how much higher its energy gets


Transition metal complex bonding and spectroscopy review

Example: Linear shape: ligands at positions 1 and 6dz2 dx2-y2dxydxzdyz1+1 0 0 0 0

MO Diagram:


Transition metal complex bonding and spectroscopy review

Example: Square pyramid shape: ligands at positions 1, 2, 3, 4, 5dz2 dx2-y2dxydxzdyz1+4(1/4) 4(3/4) 0 0 0

MO Diagram:


Counting d electrons count over from group 1a size of positive charge ti 2 v co 3

Counting d electrons: Count over from Group 1A – size of positive chargeTi2+:V+:Co3+:


Filling in electrons

Filling in Electrons

If gap is >=2, then need to consider high/low spin.

If gap is <2, then it is always high spin.

MO Diagram examples:


Comparing overall bond order low spin case

Comparing Overall Bond Order: Low spin case

Square pyramid d6 case:

Oh d6 case:


Comparing overall bond order high spin case

Comparing Overall Bond Order: High spin case

Square pyramid d6 case:

Oh d6 case:


Spectroscopy 3 types of transitions 1 d d transitions wavelength vs bond strength 2 lmct 3 mlct

Spectroscopy: 3 types of transitions 1. d-d transitions wavelength vs. bond strength 2. LMCT 3. MLCT


Transition metal complex bonding and spectroscopy review

Sigma Interaction Strength


Transition metal complex bonding and spectroscopy review

LMCT with Pi Donor Ligands: Mainly oxides and halides


Transition metal complex bonding and spectroscopy review

MLCT with Pi Acceptor Ligands and spectroscopy: CO, CN-, pyridine


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