3d Metal Complexes

Synthesis, Spectroscopic, Electronic, and Magnetic Properties

By Mark Justine R. Zapanta

What were going to talk about 1. Introduction to transition metals 2. Nomenclature 3. Isomerism in coordinate compounds 4. Interpretation of metal complexes spectra 5. Overview of bonding in transition metals 6. Crystal Field Theory 7. Magnetic susceptibility 8. Ligand Field Theory 9. Charge Transfer 10. Electron Transitions 11. Selection rules 12. Tanabe-Sugano Diagram WERE NOT GOING TO TALK ABOUT MOLECULAR MODELING (I.E. MINIMIZED ENERGY)!

What are transition metals? elements that have at least one simple ion with an incomplete outer set of d electrons

d-block metals that are not transition metals Zinc Zn Zn2+ [Ar] 4s23d10 [Ar] 3d10 (definition is not satisfied)

Scandium Sc Sc2+ [Ar] 4s13d1 [Ar] (definition is not satisfied)

Naked transition metals? Probably not.

Transition metal ion is usually covalently bonded to other ions or molecules

Metal ion Lewis acid Ligand Lewis base

Whats in a name? Nomenclature rules

Whats in a name? Nomenclature rules

Whats in a name? Nomenclature rules

Whats in a name? Nomenclature rules

Isomerism in transition metal complexes

Orbital splitting and electron spin

Structural isomers
1. Ionization isomers [PtBr(NH3)3]NO2 and [Pt(NO2)(NH3)3]Br 2. Linkage isomers [Co(ONO)(NH3)5]Cl and [Co(NO2)(NH3)5]Cl

3. Coordination isomers [Co(NH3)6] [Cr(C2O4)3] and [Co(C2O4)3] [Cr(NH3)6]

4. Hydrate isomers [CrCl2(H2O)4]Cl2H2O Crystal Field Stabilization Energy [CrCl(H O) ]Cl H O 2 5 2 2 Crystal Field Splitting [Cr(H2O)6]Cl3

Orbital splitting and electron spin

Geometric isomers
1. Cis and trans

2. Fac and mer

Optical isomers non-superimpossable mirror image

Crystal Field Stabilization Energy Crystal Field Splitting

Overview of bonding theories of transition metals

Assumed that bonding of transition metals was similar to that of typical main group elements assigning different modes of hybridization to the metal ion depending on the known geometry of the compound

Valence Bond Theory

Crystal Field Theory

Assumed that the interaction between a metal ion and its ligand was totally electrostatic in nature

Ligand Field Theory

Modified form of CFT. Takes the covalent character into account Racah parameter (B)

Molecular Orbital Theory

Most sophisticated theory Not necessary for the discussion of conventional transition metal complexes

A simple approach to Crystal Field Theory

Crystal Field Stabilization Energy Crystal Field Splitting

Orbital splitting and electron spin

strong ligand field = large = low spin

weak ligand field = small = high spin

Crystal Field Stabilization Energy Crystal Field Splitting

Magnetic susceptibility Diamagnetic no unpaired electron slightly repelled by magnetic field Paramagnetic has unpaired electron attracted into magnetic field Magnetic susceptibility measure of magnetism s = 2 [S(S+1)]^.5 = [n(n+2)]^.5

Crystal Field Stabilization Energy Crystal Field Splitting

A challenging approach: Ligand Field Theory

Pi bonding Addition of other ligand orbitals allows the possibility of pi bonding

The ligand must have a p orbital or pi* molecular orbitals

Types: 1. pi-acceptor ligands -empty pi* orbitals

2. pi-donor ligands

Pi bonding

Crystal Field Theory Crystal Field Splitting depends on four factors: 1. Identity of the metal first row < second row (50%) < third row (25%) 2. Oxidation state of the metal higher oxidation state 3. Number of ligands greater for more ligands 4. Nature of ligands spectrochemical series

Charge Transfer Ligand to Metal Charge Transfer

Transfer of e-s from MO with primary character of a ligand to orbital that are primary metal in character formal reduction of the metal MnO4-

Charge Transfer Metal to Ligand Charge Transfer

pi* orbitals on the ligands (pi-acceptor ligand) become the acceptor orbitals on the absorption of light oxidation of the metal CO, CN-, SCN-

Electronic spectra of coordination compounds Electronic transition absorption bands Complementary

Selection rules Laporte selection rule transition between states of the same parity is forbidden In Oh symmetry, d to d transitions are forbidden!

Relaxation: bond vibration removes symmetry, orbital mixing

Selection rules Spin selection rule transition between states of different spin multiplicities is forbidden Relaxation: spin-orbit coupling

Interpreting the spectra

Tanabe-Sugano Diagram
a correlation diagram

plot of E/B vs. /B

B = Racah parameter -measure of the repulsion b/w terms of the same multiplicity Free-ion term describe the energy levels of a free dn ion in the absence of any interactions with ligands

Interpreting the spectra Tanabe-Sugano Diagram we can often obtain values and sometimes B of reasonable accuracy simply by using the positions of the absorption maxima taken directly from the spectra simplest cases: d1, d4 (h.s.), d6 (h.s.), d9

Interpreting the spectra

Interpreting the spectra

What are those shoulders? Jahn-Teller Effect there cannot be unequal occupation of orbitals with identical energies

Interpreting the spectra Cases: d3, d8 T2g A2g corresponds to

Interpreting the spectra Cases: d2, d7 h.s. A2g T2g corresponds to

QUESTIONS?

Comments: 1. In the magnetic susceptibility part, discuss how to calculate for spin-only