1. Review of Crystal Field Theory. Crystal Field Stabilisation Energies: origin and effects on structures and thermodynamic properties. Introduction to Absorption Spectroscopy and Magnetism. The d1 case. Ligand Field Theory and evidence for the interaction of ligand orbitals with metal orbitals.

2. Spectroscopic properties of first row transition metal complexes.
a) Electronic states of partly filled quantum levels. l, ml and s quantum numbers. Selection rules for electronic transitions.
b) Splitting of the free ion energy levels in Octahedral and Tetrahedral complexes. Orgel and Tanabe-Sugano diagrams.
c) Spectra of aquated metal ions. Factors affecting positions, intensities and shapes of absorption bands.

3. Magnetic Susceptibilities of first row transition metal complexes.
a) Effect of orbital contributions arising from ground and excited states.
b) Deviation from the spin-only approximation.
c) Experimental determination of magnetic moments. Interpretation of data.

4. General properties (physical and chemical) of the 3d transition metals.
Periodic trends in stabilities of common oxidation states.
Contrast between first-row elements and their heavier congeners.

5. A survey of the chemistry of some of the elements Ti....Cu,
which will include the following topics:
a) Occurrence, extraction, biological significance, reactions and uses
b) Redox reactions, effects of pH on the simple aqua ions
c) Simple oxides, halides and other simple binary compounds.
d) Preparation, structures, physical properties, reactions, uses of a variety of simple coordination complexes, eg acacs, acetates, amines, etc.

6. Reaction Mechanisms. Stability and inertness, rates and mechanisms. Classification of inorganic reaction mechanisms. Molecularity in relation to substitution reactions. Square planar substitution; evidence for the 'A' mechanism. The trans effect. Octahedral substitution: aquation, anation and base hydrolysis. Electron transfer reactions - inner/outer sphere.

7. Transition metal organometallics. Carbonyls and other p-acceptor ligands; syntheses, structures and bonding and reactions. The EAN rule. Organic ligands: alkyls, alkenes, p-allyls and aromatic ligands including cyclopentadiene. A discussion of synthetic methods, structural and bonding aspects, physical properties, stabilities and important reactions. Catalysis and important industrial uses.

References:
"Complexes and First-Row Transition Elements", Nicholls
"Basic Inorganic Chemistry", Cotton, Wilkinson and Gaus
"Advanced Inorganic Chemistry", Cotton and Wilkinson
"Coordination Compounds", Kettle
"Chemistry of the Elements", Greenwood and Earnshaw
"Concepts and Models of Inorganic Chemistry", Douglas, McDaniel and Alexander

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Created Jan 99. Last modified 20th January-99.
URL http://wwwchem.uwimona.edu.jm:1104/courses/C21Jout.html