The module will be delivered in 44 1-hour lectures, 6 1-hour workshops and 4 1-hour tutorials.  There will also be a 2-hour revision session.

A written exam will test the student’s knowledge and understanding as elaborated under the learning outcomes. The coursework will allow the student to demonstrate his/her ability to judge and critically review relevant information.

Autumn

2^nd and 3^rd row transition metal coordination chemistry

Lanthanide contraction: origin and consequences.

Systematic survey of heavy transition metal compounds.

Trends in reactivity and structure of halides, oxides/oxoanions; more detailed look at representative compounds.

Mixed-valence species.

Metal-metal bonding

Syntheses, structures and metal-metal bonding in transition metal dimers, trimers and larger clusters.

Detailed discussion of rhenium- and molybdenum-based systems.

Multiple metal-metal bonds.

Electronic properties of stacked platinum complexes (e.g. Magnus’s salt) and anisotropic conduction.

Magnetochemistry

Magnetic properties of lower symmetry complexes:TBP, trigonal and trigonal prismatic.

Organometallic examples.

Non-dilute systems.

Multimetallic systems.

Exchange mechanisms: for design or for rationalising systems.

Exchange integral: measuring for d⁹ systems.

Complexes with co-ordinated radicals:

Innocent and non-innocent ligands.

Examples considering magnetic, electrochemical and EPR properties.

Orbital contributions:

Nature of A and E term complexes and TIP;

Nature of T terms: Kotani plots and their derivation.

Elucidation of geometry utilising magnetic data.

Effect of paramagnetism on NMR; contact shift; shift reagents; Evans’ method.

Spring

Structure and bonding in organometallic chemistry

Description of bonding models for π-acceptor ligands, including CO, alkenes (Dewar Chatt Duncanson model) and tertiary phosphines.

Physical evidence and consequences of bonding, applications of infrared spectroscopy.

Other σ-bonding ligands, e.g. N₂, NO and O₂ ligands.

Metal carbonyl complexes, preparation, properties and structure.

Bonding and structure in metal alkene complexes including conjugated anionic and polyalkene ligands and influences upon reactivity.

Metal alkyl compounds (carbon π-bonded compounds).

Metal carbon multiply bonded systems, carbene (Fischer type) and alkylidene/alkylidyne (Schrock type) compounds.

Examination of bonding models for these systems and relationships with experimentally observed reactivity, significance in applications (e.g. alkene metathesis).

Formation and properties of transition metal compounds with metal carbon bonds.

Transition metal hydrides and dihydrogen complexes.

Spectroscopic techniques of study of organometallic compounds (e.g. NMR etc.).

Mechanistic organometallic chemistry

Classic reaction pathways of organometallic compounds, introduction to catalytic cycles

Oxidative additions, reductive eliminations, migratory insertions, hydrogen migrations.

Reactions of metal-alkene, metal-CO and metal-alkyl complexes relevant to homogeneous catalysis and a discussion of mechanisms (hydrogenation, carbonylation, polymerisation, metathesis, cross-coupling, asymmetric catalysis).

An indicative reading and resource list will be included in the Course Handbook.

An indicative reading and resource list will be included in the Course Handbook.