Module Details
The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.
Title INORGANIC CHEMISTRY III
Code CHEM311
Coordinator Dr AM Fogg
Chemistry
Year CATS Level Semester CATS Value
Session 2008-09 Level Three First Semester 15

Aims

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 CnHn (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 behaviour of doped semiconductors. 

Learning Outcomes

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.

Syllabus
0 

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 systems, CO, PR3 and H complexes. H2 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. Fogg 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 2Cu3O7 structure as a perovskite superstruc ture, 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 model.

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 (Id 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 reactions (e.g. anation): the Eigen-Wilkins ideas. Mechanisms at special, inert 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.

                                                                                                


Teaching and Learning Strategies

Teaching and Learning Strategies:

This module consists of 30 50-minute lectures.  These lectures will be supported by five small group tutorials at times to be arranged. In addition, students will be expected to spend at least 10 hours on the extended essay.  Students should expect to spend at least six hours per week in private study related to this module.


Teaching Schedule
  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 26

   5

       31
Timetable (if known)              
Private Study 119
TOTAL HOURS 150

Assessment
EXAM Duration Timing
(Semester)		 % of
final
mark		 Resit/resubmission
opportunity		 Penalty for late
submission		 Notes
Written Examination  3 hours  First  65  August resit opportunity for PGT students only, where applicable. See notes     Yr 3 & Yr 4 resit at next normal opportunity  
CONTINUOUS Duration Timing
(Semester)		 % of
final
mark		 Resit/resubmission
opportunity		 Penalty for late
submission		 Notes
Tutorials    First  20  none  Standard University Policy applies - see Department/School handbook for details.  Students will be marked on their attendance and submitted work. Annonymous marking impossible  
Essay    First  15  none  Standard University Policy applies - see Department/School handbook for details.  Students will be required to produce a presentation on the work of a prominent scientist from the history of inorganic reaction mechanism determination. This work is not marked anonymously  

Recommended Texts
  • D.F. Shriver and P.W. Atkins, "Inorganic Chemistry" (3rd edition), OUP Oxford 1999, ISBN (paperback) 0 19 850330X;

Background/ Supplementary Reading

  • Organometallics 1: complexes with transition metal carbon σ-bonds" M. Bochmann and F Bochner, Oxford University Press, 1994.
  • "Organometallics 2: complexes with transition metal carbon π bonds" M. Bochmann, Oxford Universty Press, 1994.
  • "Organometallics, A Concise Introduction" C Elschenbroich and A Salzer. VCH New York, 1989.
  • "Advanced Inorganic Chemistry", F.A. Cotton and G. Wilkinson. 5th Ed. Wiley New York, 1988.
  • "Inorganic Materials Chemistry" M. T. Weller. Oxford University Press, 1994.
  • "Solid State Chemistry: An Introduction" L . E. Smart and E. A. Moore. Taylor and Francis, 2005.