The aims of the module are: To rationalise the vast range of pseudo-first order rate constants found for ligand exchange among metal ions from across the Periodic Table. To outline key mechanisms by which transition and non-transition metal ions undergo ligand exchange in solution. To outline and rationalise the chemistry of complexes with metal-alkyl and metal-carbene bond. To outline and rationalise the chemistry of transition-metal complexes containing metal to carbon s-bonds, eg metal-alkyl, metal-acetylide, metal-vinyl, and metal-carbene complexes. To show how metals coordinate to compounds such as alkenes, alkynes, allyls and conjugated p-systems C n H n (n = 5 to 8) via interactions with the C-C multiple bonds. To provide an introduction to the structures of solid state materials and the role of diffraction in studying these structures. To explain how electrons behave in extended structures, with particular reference to the distinction between metals and insulators, and the b ehaviour of doped semiconductors.

(LO1) By the end of the module, students should be able to: Demonstrate an understanding of how ligand field and other factors help determine both the rate and the mechanism of ligand exchange for a given metal ion. Critically assess the role of a prominent scientist in the history of inorganic reaction mechanism investigations. Appreciate the bonding of different organic fragments to transition metals and how a variety of physical measurements can be used to substantiate these ideas. Demonstrate an understanding of the concepts of infinite solids and their diffraction of X-rays. Appreciate the factors affecting the electronic properties of solids.

Teaching Method 1 - Lecture
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Attendance Recorded: Not yet decided

Teaching Method 2 - Tutorial
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Attendance Recorded: Not yet decided

1 Organometallic Compounds Containing Metal -Carbon Bonds with σ - and/or π -bonds (10 lectures by Dr J. Iggo jointly with CHEM313) Revision and extension of Year 2 material including electron counting system s , CO, PR 3 and H complexes. H 2 complexes Synthesis, characterisation and reactivity of complexes containing metal-carbon single bonds; metal alkyl, metal-acetylide, metal-vinyl complexes. Activation of C-H bonds, C-C bond forming reactions. Synthesis, characterisation and reactivity of complexes containing metal-carbon double bonds; metal carbenes and carbynes Synthesis, characterisation and reactivity of p-bonded systems; metal alkene and metal alkyne complexes. C-C bond forming reactions, olefin metathesis and ROMP Synthesis and characterisation of metal allyl and diene complexes. Reactions and fluxionality, ring whizzers, cyclic p-bonded systems; metal cyclopentadienyl and metal arene complexes Introduction to Solid State Chemistry (10 lectures by Dr A. M. Fog g jointly with CHEM313) Diffraction and Related Techniques: Lattices and structures. Unit cells - primitive and centered. Miller indices. Diffraction. Braggs Law. Indexing Powder Patterns. Structural Chemistry: Simple structures derived from cubic and hexagonal close packing of spheres. Construction of the perovskite structure from cubic close packing. Cation and vacancy ordering YBa 2 Cu 3 O 7 structure as a perovskite superstructure, spinel and pyrochlore Electrons in Solids: Qualitative description of distinction between metals and insulators, using analogies with atomic and molecular electronic structure. Density of states and Fermi energy, and experimental evidence for these concepts. Carrier density and temperature dependence of conductivity. Electronic structure of simple metals and transition metals. Semiconductors -temperature dependence of conductivity, p and n doping, silicon versus III/V systems, band gap manipulation. Mott-Hubbard insulators and the breakdown of the band m odel. Transition Metal Chemistry (6 lectures, Dr. S. J. Higgins, jointly with CHEM313) Some basic ideas and nomenclature for inorganic reaction mechanisms: classification according to stoichiometric (A, I and D) and intimate mechanism (I d and I a ). What sort of evidence helps us decide which mechanism applies? rate laws. Activation enthalpy, entropy and volume. A special case first; ligand substitution in square planar complexes. Why Pt(II)? Rate law. Varying (i) leaving group, (ii) entering group. Varying non-leaving ligands.· Stereospecificity of the reactions: the mechanism, taking the experimental facts into account. The trans effect. The trans influence. Ligand exchange at octahedral centres. Introduction; reminder of basic CFT ideas. Rates of water exchange for metal aquo ions, and factors (charge/size, CFSE) affecting this. Volumes and entropies of activation, and mechanistic conclusions. Experimental evidence for mechanisms in Co(III) chemistry. Extensions to other react ions (e.g. anation): the Eigen-Wilkins ideas. Mechanisms at special, inert centres; Co(III) and Cr(III) chemistry.· Evidence for I d or D mechanisms in this chemistry: linear free energy relationships and consequences. Stereoselectivity in ligand exchange. Acid and base catalysed mechanisms; the D cb mechanism.