This module will focus on the structure, influence, and design of ligands in the development of functional metal complexes and main-group compounds. 

Three areas will be covered, representing a cross section of pertinent problems in this area, these will be: 

(a) the chemistry and catalytic applications of d0 metal complexes;  

(b) the study of N-heterocyclic carbene complexes and their catalytic chemistry; 

(c) the stoichiometric and catalytic reactions of frustrated Lewis pairs.   

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. 

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

• 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. 

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

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

The module will be delivered in 10 2-hour lectures and three 1-hour tutorials. 

The module consists of three distinct blocks, each covering a different aspect of advanced ligand design and coordination chemistry.  

The three blocks will mirror the three sections described above:  

(a) catalysts based on d0 metal complexes;  

(b) N-heterocyclic carbene complexes in catalysis;  

(c) the catalytic chemistry of frustrated Lewis pairs.  

Each block will be followed by a tutorial in which problem-solving and analytical skills are practised. 

Chemistry-Specific Skills: 

• Students will already know how to construct a catalytic mechanism for simple catalysts and substrates (level 6); in this module students will learn how to analyse complex datasets and to formulate an explanation for trends and observations of chemical reactivity patterns 

• Develop a level of understanding closer to situations expected in graduate-level employment.  

• Students will refine their problem-solving skills in situations that require them to synthesise a coherent argument or explanation using knowledge/data from a number of different sources. 

Employability skills:    

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

• Contribute to discussions, negotiate, and present with impact.  

• 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:    

 Coursework                      30% 

• Contribute to discussions, negotiate, and present with impact.  

• 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. 

 Exam                                70%  

• Contribute to discussions, negotiate, and present with impact.  

• 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. 

•  

 Resit Exam                      100%  

• Contribute to discussions, negotiate, and present with impact.  

• 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. 

• . 

Sustainable Development Goals:     

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

Goal 6. Ensure availability and sustainable management of water and sanitation for all. 

Goal 12. Ensure sustainable consumption and production patterns. 

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

Formative assessment will be provided in the three tutorial sessions following each of the three theory blocks. These tutorials will be interactive and will develop the problem-solving skills required to apply the core lecture material to unfamiliar situations.

Summative assessment will take the form of coursework (20%) and written examination (80%). Coursework will consist of a single piece of work of three 10-mark questions; each question will be problem-based and will require students to apply concepts of ligand design to synthesise catalytic mechanisms within unfamiliar operating parameters. This will allow students to meet learning objectives 1 and 2.

The examination will consist of four 20-mark questions; students must answer any three. Questions will probe students’ ability to interpret data and to construct mechanistic arguments based on provided data, thus allowing students to meet learning objectives 3-4. 

Marking criteria 

50-60 Satisfactory appreciation of the key concepts of catalyst design and their structural influence on catalytic reactions. Work in this category will demonstrate the ability to design catalytic cycles to an unfamiliar substrate and/or catalyst that are similar (but not identical) to those given in lecture material. There will also be a demonstrable ability to construct a ligand and/or catalyst synthesis from the molecular types illustrated in the lecture material.

60-70 Good grasp of most concepts relating to catalyst performance in relation to catalyst and substrate structure. Will demonstrate the ability to relate material from across all areas of the course to synthesise a rational explanation for catalyst performance and chemical reactivity. Will be able to propose a more advanced chemical synthesis pathway and an appreciation for how analytical techniques can aid the understanding of catalyst performance.

70-100 Excellent demonstration of catalyst design and structural influence on catalytic reactions. An outstanding ability to make connections between different areas of knowledge to aid a thorough interpretation of unfamiliar data, providing a rigorous spectroscopic/mechanistic/structural analysis. The ability to demonstrate appropriate weighting in different parameters that can affect chemical reactivity as applied to an unfamiliar situation. 

THE OPPORTUNITY FOR REASSESSMENT IN THIS MODULE: 

Opportunities for re-assessment is only permitted provided you have not failed more credit than in the resit rule adopted by your programme. If the amount of credit you have failed is more than permitted by the relevant resit rule, you may be permitted to repeat study if you are within the threshold set for the Repeat rule adopted by your programme. You will be notified of your eligibility to resit/repeat any modules after the Examining Board in the Summer period.

All resit assessments will be held in the Resit Examination period, prior to the start of the following academic session. 

The resit examination will adopt the same format as the main examination but will contain questions that allow students to demonstrate learning objectives 1-4. 

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 properties of d0metals in 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. 

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. 

N-heterocyclic carbenes 

- Introduction to N-Heterocyclic Carbenes (NHC) as ligands and their complexes with transition metals, providing knowledge of the routes to their synthesis as well as on their structure, reactivity, and electronic/steric properties. The scope and advantages of metal NHC compounds and their application in catalysis. 

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.