This module will focus on the structure, influence, and design of ligands and compounds in the development of functional metal complexes and main-group compounds.  Four areas will be covered, representing a cross section of pertinent problems in this area, these will be a) metal complexes for catalytic polymerisation and depolymerisation; b) the study of N-heterocyclic carbene complexes and their catalytic chemistry; and c) the stoichiometric and catalytic reactions of frustrated Lewis pairs; d) advanced aspects of homogeneous catalysis for sustainable chemical synthesis.  The module will cover the synthesis of ligand precursors, coordination chemistry, including in cases where there is no electronic preference to coordination geometry, and homogeneous catalysis.  Attention will be given to the analysis of structure-activity relationships and the interpretation of catalytic data in terms of reaction mechanisms. The module highlights the use of inorganic chemistry for sustainable chemical processes and aligns with UN STGs 9, 11, 12, 13, 14, and 15. 

1. Formulate a catalytic reaction mechanism within unfamiliar operating parameters (e.g. catalyst and/or substrate structure). 

2. Critically evaluate catalytic reaction data in terms of the likely reaction mechanism, substrate structure, and catalyst design; assess structure-reactivity effects of ligands and formulate reactivity patterns. 

3. Design an appropriate synthetic strategy for ligands and complexes within provided constraints. 

4. Choose appropriate analytical techniques to characterise chemical species and assess analytical data in terms of chemical structure. 

The module will be delivered in 20 2-hour lectures and four 1-hour tutorials. 

The module consists of four distinct blocks, each covering a different aspect of advanced inorganic and coordination chemistry. The four blocks will mirror the three sections described above: (a) the production and chemical recycling of polymers, including traditional polyolefins and modern alternatives; (b) metal complexes bearing N-heterocyclic carbene ligands in catalysis for sustainable chemical synthesis; (c) the role of frustrated Lewis pairs in catalysis; and (d) modern aspects of coordination chemistry relating to catalysis. Each block will be followed by a tutorial in which problem-solving and analytical skills are practised. 

Chemistry-specific skills: 

• Learn how to analyse complex datasets and to formulate an explanation for trends and observations of chemical reactivity patterns.  

• Develop the ability to relate the fundamental properties of functional metal complexes to a modern understanding of sustainable chemistry. 

• Learn how to construct a cost-benefit analysis of making chemical processes aligned to the UN Sustainable Development Goals.  

• Develop problem-solving skills in situations that require them to synthesise a coherent argument or explanation using knowledge/data from several different sources, particularly relating to chemical processes involving metal complexes. 

Employability skills: 

This module is delivered and aligns with the following University Graduate Attributes:  

• Consider own personal and professional ethical, social and environmental responsibilities. 

• Demonstrate personal and professional integrity, reliability and competence. 

• Be mindful of the Climate Emergency and the UN's Sustainable Development Goals 

• Identify, define and analyse complex issues and ideas, exercising critical judgment in evaluating sources of information. 

• Demonstrate intellectual curiosity and engage in the pursuit of new knowledge and understanding. 

• Investigate problems and offer effective solutions, reflecting on and learning from successes and failures. 

• Generate original ideas and apply creative, imaginative and innovative thinking in response to identified needs and problems. 

• Actively reflect on own studies achievements and self-identity 

• Demonstrate resilience, adaptability and creativity in dealing with challenges, and be open to change. 

• Identify and articulate own skills, knowledge and understanding confidently and in a variety of contexts. 

• Engage with new ideas, opportunities and technologies, building knowledge and experience to make informed decisions about own future.  

Graduate attributes – assessment: 

Written assessment (100%) 

• Contribute to discussions, negotiate and present with impact. 

• Identify, define and analyse complex issues and ideas, exercising critical judgment in evaluating sources of information. 

• Demonstrate intellectual curiosity and engage in the pursuit of new knowledge and understanding. 

• Investigate problems and offer effective solutions, reflecting on and learning from successes and failures. 

• Generate original ideas and apply creative, imaginative and innovative thinking in response to identified needs and problems. 

• Demonstrate resilience, adaptability and creativity in dealing with challenges, and be open to change. 

• Identify and articulate own skills, knowledge and understanding confidently and in a variety of contexts. 

Sustainable development goals: 

This module is delivered and aligns in working towards the following Sustainable Development Goals: 

Goal 9. Build resilient infrastructure, promote inclusive and sustainable industrialisation and foster innovation. 

Goal 11. Make cities and human settlements inclusive, safe, resilient and sustainable. 

Goal 12. Ensure sustainable consumption and production patterns. 

Goal 13. Take urgent action to combat climate change and its impacts. 

Goal 14. Conserve and sustainably use the oceans, seas, and marine resources for sustainable development. 

Goal 15. Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse biodiversity loss. 

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

The past and future of polymerisation catalysis 

A detailed mechanistic understanding of the properties and reactivity of d0 metal alkyl and alkyl cations will be discussed.  These complexes have most widely studied in the context of alkene polymerisation, and this type of reactivity will be used to exemplify the reactivity of d0 complexes.  The level of detail moves on from that covered in level 6, encompassing the catalyst structures required for the production of stereospecific polymers and the influence of agostic interactions to facilitate migratory insertion reactions.  This theme will be expanded to introduce the polymerisation of cyclic esters, commonly used as biodegradable polymers, and then ultimately to the forefront of polymerisation research where ring-opening co-polymerisation of CO2/epoxides and anhydrides/epoxides will be covered in detail. Approaches for depolymerisation catalysis by metal complexes will be covered. 

Heterofunctionalisation catalysis 

The role of d0metal complexes as catalysts for a range of organic transformations will be discussed, with particular focus on hydroamination, hydrogenation, hydrosilylation, and hydrophosphination.  A particular focus will be given to looking at the mechanisms of these reactions, for which there are less reaction steps possible (e.g. oxidative addition is precluded). This theme will be expanded to cover alkaline earth metals in catalysis, including their environmental benefits, their scope, and their limitations. 

Homogeneous catalysis in the 21st century 

This part of the module considers how established homogeneous catalytic systems can be improved in terms of both cost and environmental impact.  In particular, application of the principles of ‘green catalysis’ will be emphasised with regard to the nature of the catalyst, the chemical process itself and greener alternatives to established materials. The development of N-heterocyclic carbenes will be discussed, in relation to their synthesis, coordination chemistry, and catalytic applications. Comparisons will be drawn between NHC complexes and those bearing alternative ligands. 

p-Block organometallics 

Introduction to p-block organometallics, including structure and reactivity trends will be provided. This will lead to a detailed discussion of frustrated Lewis pairs (FLPs), and their role in catalysis.