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.
Code CHEM313
Coordinator Prof SJ Higgins
Year CATS Level Semester CATS Value
Session 2016-17 Level 6 FHEQ First Semester 15

Pre-requisites before taking this module (or general academic requirements):

Completion of years 1 and 2 of an MChem or BSc (Hons) Chemistry programme or, for PGT students, a non-University of Liverpool BSc (Hons) Chemistry programme.  


The aims of the module are:

  • To explain the mechanisms by which transition metal complexes exchange ligands, and how they participate in redox reactions.
  • 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
  • T o 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 the role of ligand field and other factors in determining how metal complexes undergo ligand exchange, and how they undergo electron transfer.
  • 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 and Learning Strategies

Lecture -

Tutorial -



Organometallic Compounds Containing Metal -Carbon Bonds with σ - and/or π -bonds (10 lectures by Dr J. Iggo jointly with CHEM311)

  • 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
  • Syn thesis, 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 CHEM311)

  • 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 2Cu3 O7 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 model.

Inorganic Reaction Mechanisms: Ligand substitution reactions ( 6 lectures, Dr S. J. Higgins, only for CHEM313)

  • Some basic ideas and nomenclature for inorganic reaction mechanisms: classification according to stoichiometric (A, I and D) and intimate mechanism (Id and Ia).
  • 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.

Inorganic Reaction Mechanisms: Redox reactions of metal complexes. (4 lectures, Dr S. J. Higgins, only for CHEM313)

  • 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.
  • Inner sphere mechanism: Evidence. Application in synthesis. Mixed valence complexes. Robin and Day classification

Recommended Texts

Reading lists are managed at Click here to access the reading lists for this module.
Explanation of Reading List:

Teaching Schedule

  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 35


Timetable (if known)              
Private Study 110


EXAM Duration Timing
% of
Penalty for late
Unseen Written Exam  3 hours  First  80  Yes  Standard UoL penalty applies  Assessment 2 Notes (applying to all assessments) Five problem sets will be set during the semester which will be assessed with the questions being discussed in tutorials. Annonymous marking is impossible for these problem sets. August resit for PGT students if applicable. Integrated Master's students resit at the next normal opportunity.  
CONTINUOUS Duration Timing
% of
Penalty for late
Coursework  5x4 hr problem sets  Semester 1  20  No reassessment opportunity  Standard UoL penalty applies  Assessment 1 There is no reassessment opportunity,