Towards a Series of Design Rules for Homogeneous Catalysis: Synergy Between Experiment and Theory

Lead Research Organisation: Queen Mary, University of London
Department Name: Sch of Biological and Chemical Sciences


Despite currently shrinking energy supplies and growing industrial environmental impact, demand continues to rise for products manufactured under forcing conditions (eg. high temperature, pressure), often in the presence of toxic solvents. Industry is continually searching for novel means to reducing production expense and environmental impact. The lack of transferability between existing solutions entails starting anew for each class of reactions. Rational design and optimisation of efficient catalysts presents a solution; it also represents one of the ultimate challenges in the molecular sciences, particularly for homogeneous systems. Catalysis has the highest industrial and environmental impact, opening up never-before-possible ways of creating new bonds and compounds besides imparting pollution reduction and energy efficiency to existing processes.A proposal is made to initiate a novel research line to establishing a central methodology towards characterising homogeneous cross-coupling catalysts, by experiment and theory, towards adding to a growing body of 'design rules' thereof. Focus involves the theoretical characterisation of 2 differing cross-coupling mechanisms. Subsequent wavefunction and electronic structure analyses will be carried-out jointly with collaborators. Both the desired product (cross-coupling) and main side-product (arising from beta-hydride elimination) formations will be studied, for selected Ni and Pd-containing systems. Catalyst samples as well as complexes and variations thereof will be synthesised and their reactivities characterised by project collaborators. Results will aid the candidates concurrent pioneering of theory-designed neutron spectroscopy (NS) experiments to quantify substituent alkyl-group dynamics and their coupling to catalyst flexibility, substrate coordination and electronic structure at the catalytic centre.An EPSRC award would be strategic in helping the candidate contribute to the rational optimisation and design of cross-coupling catalysts and to extend the application of NS. The project would be instrumental in establishing the candidate as a world authority in the theoretical and spectroscopic characterisation of existing homogeneous catalysts and design of novel catalysts.This is a demanding project with the objective of advancing the rational design of highly active cross-coupling catalysts, apriori using computation. Therefore, a fundamental understanding at the molecular level of the steric and electronic nature of the ligand and metal centre is essential. Since most organic reactions take place in solvent and not in a vacuum or a static dielectric field, it is pivotal (no matter how challenging!), to develop an accurate method for including the effect of solvent. As the candidate has already co-authored several high-impact publications in this area, this project will focus on the realisation of catalysed reactions in the presence of a reliable explicit solvent model. The findings of the above program of research will be of vast interest to the wider physical, theoretical, synthetic and industrial communities, as witnessed by the recent publicity detailed from ISI Web of Science searches and the candidate's own co-corresponded work highlighted in the September 2009 issue of C&E News.

Planned Impact



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Jenkins S (2015) Quantum topological resolution of catalyst proficiency in International Journal of Quantum Chemistry

Related Projects

Project Reference Relationship Related To Start End Award Value
EP/H030077/1 28/07/2010 30/09/2011 £99,972
EP/H030077/2 Transfer EP/H030077/1 01/03/2012 30/06/2012 £33,472
Description This work allowed us to characterise the structure and motions of industrially important catalysts. These catalsysts are essential in the manufacture of a wide range of products, yet also generate toxic side-products. We endeavoured to udnerstand the mechanism by which the catalysts generate desired product, or become side-tracked onto wasteful pathways to generate pollutants.

The work has resolved motions that are requisite to populating desired product pathways - almost like an atomic dance, in which the host catalyst 'leads' the partner chemicals to their final poses.

FURTHER - the work has led to the awardee applying the findings to problems in materials science - specifically on cementation mechanisms, involving acid-catlysed reactions with glass fillers to form biocompatible implant materials.
Exploitation Route The general findings of motion-driven selectivity in catalysis is transferable to other industrially important areas such as novel functional and construction materials, wherein properties are determined by such motions.

The work has proven itself as applicable to other systems and phenomena, with successful and impacting outputs in materials science; specifically for acid-catalysed cementation reactions.

Sectors Agriculture, Food and Drink,Chemicals,Construction,Education,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

Description The findings of our work have been cited over 70 times in the multiple publications generated from this project. These papers have been used by fellow academics in the UK and EU/EEA as well as in the rest of the world, including some practiioners of industrial chemical technology.
First Year Of Impact 2011
Sector Chemicals,Education,Electronics,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology
Impact Types Cultural,Economic

Description Royal Society Internal Research Exchanges
Amount £12,000 (GBP)
Funding ID IE120096 
Organisation Royal Society of Chemistry 
Sector Charity/Non Profit
Country United Kingdom
Start 06/2012 
End 03/2014
Description QMUL - BNU 
Organisation Beijing Normal University
Country China 
Sector Academic/University 
PI Contribution We worked together very closely to generate results and to bring them forward to publication. Bi-lateral visits allowed us to evovle the collaboration into a long-term one as well as a personal udnerstanding.
Collaborator Contribution Prof. FANG is an expert in determining the electronic structure of molecular systems. In this case, his contributions and mentorship in this area allowed for highly-accurate resolution of the electronic structures in differing 'good' and 'bad' catalysts.
Impact 6 joint publication were generated directly related to this work on catalysis. A further 4 joint-paper in indirectly-related areas were likewise produced. A Royal Society of Chemistry International Research Exchange Grant was always awarded to the 2 groups (at QMUL, UK and BNU, CN).
Start Year 2009