Organometallic Compounds Containing Metal -Carbon Bonds with σ - and/or π -bonds (10 lectures by Dr J. Iggo jointly with CHEM311)
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Revision and extension of Year 2 material including electron counting systems, CO, PR3 and H complexes. H2 complexes
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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.
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Synthesis, characterisation and reactivity of complexes containing metal-carbon double bonds; metal carbenes and carbynes
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Synthesis, characterisation and
reactivity of p-bonded systems; metal alkene and metal alkyne complexes. C-C bond forming reactions, olefin metathesis and ROMP
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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. Fogg jointly with CHEM311)
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Diffraction and Related Techniques: Lattices and structures. Unit cells - primitive and centered. Miller indices. Diffraction. Braggs Law. Indexing Powder Patterns.
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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 2Cu3 O7 structure as a perovskite superstructure, spinel and pyrochlore.
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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 model.
Inorganic Reaction Mechanisms: Ligand substitution reactions ( 6 lectures, Dr S. J. Higgins, only for CHEM313)
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Some basic ideas and nomenclature for inorganic reaction mechanisms: classification according to stoichiometric (A, I and
D) and intimate mechanism (Id and Ia).
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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.
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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.
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Extensions to other reactions (e.g. anation): the Eigen-Wilkins ideas. Mechanisms at special, i
nert centres; Co(III) and Cr(III) chemistry.· Evidence for Id or D mechanisms in this chemistry: linear free energy relationships and consequences. Stereoselectivity in ligand exchange. Acid and base catalysed mechanisms; the Dcb mechanism.
Inorganic Reaction Mechanisms: Redox reactions of metal complexes. (4 lectures, Dr S. J. Higgins, only for CHEM313)
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Why important? Fundamental ideas; inner-sphere and outer-sphere mechanisms. Experiments to determine which mechanism operates. Why there is a barrier to outer-sphere electron transfer. Marcus relationship.
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Inner sphere mechanism: Evidence. Application in synthesis. Mixed valence complexes. Robin and Day classification
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