This module will focus on the structure and design of ligands in the development of functional metal complexes.  Three areas will be covered, representing a cross section of pertinent problems in this area, these will be a) the development of catalysts based upon s and f block metals; b) the study of ligand dynamics and their influence on the structure and activity of metal complexes; and c) the use of macrocyclic ligands in bioinorganic models.  The module will cover the synthesis of targeted ligand precursors, the coordination chemistry of these ligands, and their influence on specific types of reactivity.  Attention will be given to the analysis of structure-activity relationships.

Knowledge

• Show an awareness of the electronic properties of the s, d, and f block metals.
• Show an awareness of how ligand structure influences the structure of metal complexes.
• Appreciate the reactivity of metal complexes, and how this can be influenced by changes in the supporting ligands.
• Identify structure-activity relationships in coordination complexes, particularly focussing on ligand structure and coordination geometry vs. reactivity.

Understanding

• Relate the electronic structure of metals to the observed reactivity of metal complexes.
• Understand the properties of ligands, and how design features can be used to control the properties of metal complexes.
• Understand the dynamic nature of many metal complexes, and relate this to observed reactivity patterns.

This module will be delivered in 10 two-hour lectures, supplemented by 4 1-hour class tutorials, and consists of three distinct blocks, each covering a different aspect of advanced ligand design and coordination chemistry. Each block will consist of lectures supported by an assessed piece of coursework.  The three blocks will mirror the three sections described above: (a) the development of catalysts based upon s and f block metals; (b) the study of ligand dynamics and their influence on the structure and activity of metal complexes; and (c) the use of macrocyclic ligands in bioinorganic models.

Ability to analyse and review the details of ligand design and coordination chemistry, and relate these concepts to physical and chemical properties.

The module will be assessed by a combination of coursework (20%) and written examination (80%). Coursework will be broken down into 3 short, problem-based pieces of work covering each of the three sub-topics.

The applications of ligand design and coordination chemistry to a range of areas, including catalysis and bioinorganic chemistry, with an emphasis on the ability of controlling the properties and reactivity of metal complexes by ligand design.

The applications of alkaline earth metals in catalysis

The quest for reducing the cost and environmental footprint of chemical processes has fuelled the development of catalysts based upon metals other than the Noble Metals (Pt, Ir, Rh, etc.).  The advent of the alkaline earth metals, particularly Mg and Ca, for catalytic processes will be discussed, including their role in hydroamination, hydrosilylation, and hydrogenation catalysis.  The scope and limitations, as well as catalytic reaction mechanisms will be covered.

Lanthanides in polymerisation catalysis

The polymerisation of cyclic esters to afford biodegradable polymers has afforded much attention as alternatives to the ubiquitous poly(α-olefins). Lanthanides have been used most successfully in this regard.  The coordination chemistry and catalytic applications of lanthanides complexes will be discussed in this context, and will be supplemented by a comparison of main group metals (Mg, Ca, Zn, Al), which have been used alongside the lanthanide metals.

Dynamic processes                                                                                                                                        

Fluxionality in metal complexes including types of fluxional processes.

Methods used for the measurement and observation of fluxionality, and implications for structure and reactivity in dynamic molecules.

Examples of fluxional molecules including metal-Cp rings and metal-hydrides.

Macrocyclic chemistry and bioinorganic models

Thermodynamics and Kinetics of macrocyclic ligand complexes

Macrocyclic ligand syntheses – metal free and template systems

Bioinorganic models – principles

Modelling Lewis-acid base chemistry – dinuclear hydrolases

Functional models of redox systems – cyctochrome c oxidase, OEC PSII

Modelling non-innocent ligand systems – galactose oxidase, porphyrin radicals

Organotransition Metal Chemistry, from Bonding to Catalysis (Hartwig)

The Organometallic Chemistry of the Transition Metals (Crabtree)

Advanced Inorganic Chemistry (Cotton, Wilkinson, Murillo, and Bochmann)