CH3514 – Physical Inorganic Chemistry
Lecturers:
Dr B. E. Bode* and Dr J. A. McNulty
(*Module Convenor)
Aim:
To be able to apply spectroscopy for structure determination in inorganic chemistry and to understand the physical chemistry and molecular orbital theory of transition metal complexes.
Covers analysis of inorganic compounds by elemental analysis, mass spectrometry and nuclear magnetic resonance and electron paramagnetic resonance spectroscopies with particular emphasis on isotopologues and quadrupolar nuclei. This includes theory of the methods and data interpretation including identification of compounds from analytical data.
Inorganic Spectroscopy – Dr B. E. Bode
Duration:
8 hours
Aims:
To highlight useful spectroscopic methods for structure elucidation in inorganic chemistry.
Objectives:
1. To survey different spectroscopic methods and their application for determining structure and composition of small inorganic molecules and coordination complexes.
2. To survey several aspects of the use of NMR spectroscopy for structure determination in molecular inorganic chemistry:
a. Monoisotopic spin 1⁄2 nuclei( e.g.19F,31P)
b. Isotopologues involving spin 1⁄2nuclei(e.g. 29Si,129Xe)
c. NMR of and coupling to quadrupolar nuclei (e.g. 11B)
d. The effects of dynamics, quadrupolar relaxation and paramagnetic relaxation.
3. To introduce EPR spectroscopy and survey several aspects of its use for determination of electronic and molecular structure in molecular inorganic chemistry:
a. Acquisition and representation of spectra
b. Hyperfine couplings and g-values
c. Anisotropic spectra in solids.
Physical Chemistry and Bonding of Transition Metals – Dr J. A. McNulty
Duration:
7 hours
Aims:
A continuation of the chemistry of the 3d transition metals with particular focus on the thermodynamics, bonding and kinetics of reactions.
Objectives:
1. A summary of how d-orbitals affect the properties of the transition metals.
2. To understand metal ion-ligand complexation equilibria; stepwise formation and overall stability constants. Relationship of βML to KML and ΔGoML.
3. To understand the trends in βML across the period Sc – Zn and the Irving Williams maximum at Cu2+ due to Jahn-Teller effect at d9.
4. To understand how molecular orbital theory can be used to explain the properties of metal-ligand complexes.
5. To understand the origins of the chelate effect – the increase in ML with chelate ligands. To appreciate and rationalise the entropic and enthalpic factors involved – trends across the period and the link to LFSE. To understand the mode of action of chelation therapy.
6. To understand quantification of oxidation and reduction potentials and the illustration of these using Latimer and Frost-Ebsworth diagrams.
7. To appreciate that thermodynamic stability and kinetic lability are independent phenomena – not necessarily correlated. Equilibrium can be rapidly obtained irrespective of the size of KML.
8. To appreciate the range of labilities on 3d aqua metal ions and the correlation with LFSE. Definition of the terms inert and labile. Correlation of inertness with high LFAE – linked to LFSE.