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Staff Profile

Dr Simon Doherty

Senior Lecturer

  • Telephone: +44 (0) 191 208 6537
  • Address: Dr Simon Doherty
    Senior Lecturer in Organometallic Chemistry & Catalysis
    Director of NUCAT
    School of Natural and Environmental Sciences
    Bedson Building
    Newcastle University
    NE1 7RU
Background

Introduction

Dr Simon Doherty is a senior lecturer in Organometallic Chemistry and Catalysis and Director of NUCAT. He was awarded first class Hons. in Chemistry in 1987 and a PhD in 1990 for a thesis Coordination and Cluster Compounds of Primary Phosphines, both from University College London. After working as a postdoctoral researcher with Professor Arthur J. Carty at Waterloo, Canada, investigating small molecule activation and skeletal transformations of phosphinidine stabilized clusters and the reactivity of hydrocarbyl ligands on bimetallic phosphido-bridged complexes, he moved to Bloomington Indiana to work with Professor Malcolm Chisholm (FRS), preparing alkyl and alkoxide supported transition metal alkylidynes, nitrides and oxides and studying their MOCVD characteristics.

Previous Positions

1994-1995 Lecturer in Inorganic Chemistry University of Wales, Swansea

1995-2001 Senior Lecturer in Inorganic Chemistry, University of Newcastle

2001-2004 Reader in Inorganic Chemistry, Queen’s University of Belfast

2004-present Senior Lecturer in Inorganic Chemistry, University of Newcastle

Doherty has published over 110 research papers, written invited review articles, 2 invited Nature Protocols and contributed to several books, most recently a chapter entitled Homogeneous Catalysis in Ionic Liquids in the RSC Catalysis Series, Catalysis in Ionic Liquids: From Catalyst Synthesis to Applications.

 

Research

 

DOHERTY@NEWCASTLE UNIVERSITY CATALYSIS (NUCAT)

1. Phosphine Synthesis & Catalysis

The Doherty Group is firmly established as the principal and leading phosphine synthesis and catalysis research group at Newcastle University. The unifying theme in the Groups Phosphine Synthesis Team is the development of innovative synthetic methodology directed towards novel and architecturally distinct chiral and achiral mono- and bidentate phosphorus-based ligands and exploring their applications in platinum group metal catalysis. Over the past decade the group has assembled the NUCAT ligand kit which comprises a range of mono- and bidentate phosphines, these include:

  1. NUPHOS diphosphines via zirconium-mediated reductive coupling of alkynes 
  2. NU-BIPHEP diphosphines via rhodium-catalyzed [2 2 2] cycloaddition
  3. KITPHOS monophosphines via Diels-Alder cycloaddition of alkynylphosphine oxides
  4. CATPHOS diphosphines via double Diels-Alder cycloaddition to diynes
  5. NU-biaryl diphosphines via sequential Diels-Alder cycloaddition-extrusion
  6. NU-biaryl monophosphines via cross coupling of phosphonate-substituted aryl and naphthylboronate esters.

The most recent addition to the NUCAT ligand kit is the bulky electron-rich NU-dihydro-KITPHOS class of monophosphine which form highly efficient catalysts for the Suzuki-Miyaura cross coupling between a host of electronically diverse aryl chlorides and boronic acids.


2. Polymer Immobilized Ionic Liquid stabilized (PIILS) Catalysts

A team of researchers is exploring the use of polymer immobilised ionic liquids (PIILs) to improve existing catalytic transformations, for instance, enhancing reactions rate, improving catalyst lifetime, achieving multiple recycles and engineering continuous processes.  

Recent Developments

(a) POM-based PIILP Oxidation Catalysis (POM@PIILP)

A novel peroxometalate-based Polymer Immobilized Ionic Liquid Phase (PIILP) catalyst has been developed for the epoxidation of alkenes and allylic alcohols; the system can be recycled and reused up to 5 times with only a minor reduction in performance on successive cycles. The catalysts are prepared by combining a novel cation-decorated co-polymer, generated via Ring Opening Metathesis Polymerization (ROMP), with an oxidation active polyoxometalate; the resulting catalytic material is a free flowing, robust, air-stable solid. 

The concept of PIILP catalysis is currently being used to develop continuous flow systems for oxidations, carbonylations and C-C bond formation. To this end, our peroxometalate based PIILP catalyst has shown a marked enhancement in rate and selectivity for the oxidation of sulfides in continuous flow compared with conventional batch conditions.

(b) Asymmetric PIILP Catalysis (CuBox@PIILP)

Lewis acid copper-bis(oxazoline) based PIILP catalysts also show a marked enhancement in rate and selectivity, compared with their homogeneous counterparts in conventional organic solvents, across a host of asymmetric C-C bond forming reactions.

(c) Polymer Immobilized Ionic Liquid Stabilized NPs (NP@PIILS) for Green and Sustainable Catalysis

The team is also exploring how the polymer microstructure and charge density affects the size, distribution and morphology of gold, ruthenium, platinum and palladium nanoparticles and to this end we have shown that heteroatom donor modified PdNP@PIILP are highly efficient systems for Suzuki-Miyaura cross coupling, as well as the dehydrogenation of formic acid. In their most recent developmentm the group has shown that PdNP@PIILP systems are highly selective (87%) for hydrogenation of the C=C bond in a range of alpha,beta-unsaturated aldehydes and ketones and remarkably active and highly selective catalysts for the reduction of aromatic nitro compounds to N-hydroxylamines, azoyarenes and anilines while AuNP@PIILP is high selective for the partial reduction of nitroaenes to N-arylhydroxylamines and azoxyarenes. The results of our work have recently been disclosed in Green Chem. (2017, 19, 1635-1641), Catal. Sci. & Technol. (2018, 8, 1454-1467 and 2022, 12, 3549–3567), Adv. Synth. Catal. (2018, 360, 3716-3731), and ACS Catalysis (2019, 19, 4777-4791).


We are currently developing new ruthenium platinum and bimetallic NP based catalysts for the hydrolytic evolution of hydrogen from boron hydride materials and preliminary results have recently been accepted for publication (ChemCatChem 2022, DOI: 10.1002/cctc.202101752R1 and Mol. Catal. 2022, 528, 112476. DOI.org/10.1016/j.mcat.2022.112476)


The group is also developing amino modified polymers and mesoporous silicas immobilized ionic liquid as supports for Pd and PdM heterometalliic nanoparticles for the catalytic hydrogenation of CO2 to formate and our preliminary results have recently been accepted for publication in Chem. Commun. (Dec 2023). The same project is also the electrocatalytic reduction of CO2 to formate and fuels with the aim of developing an understanding of the factors that control selectivity.


In an entirely new venture we are developing new noble and non-noble metal bimetallic catalysts and polyionic liquid based membranes for application in alkaline anion exchange membrane based water electrolysers; this project involves a collaboration with Dr Mohamed Mamlouk in the School of Chemical Engineering.   


3. Phosphinoboration

Westcott and Doherty have recently teamed up in a collaboration to develop new phosphinoboronate esters for the synchronous formation of P-C and B-C/B-heteroatom bonds i.e. phosphinoboration. Reagents of the type R2P-B(OR)2 (R = Ph, Cy, tert-butyl, OR = pinacol, catechol) react readily with aldehydes, ketones, imines and enones to give the corresponding 1,2-addition products. The reagents also undergo metal catalysed regioselective addition to C-C multiple bonds in alkynes and allenes. Studies are currently under way to explore the scope of this transformation, extend the range of substrates, develop the fundamental coordination chemistry relevant to catalysis and to understand the mechanism. Results of preliminary studies have recently been accepted for publication in Angewandte Chemie (December 2014). 

 

Past and Present Collaborators

Dr J. G. Knight (Newcastle), Professor S. A. Westcott (Mount Allison, Canada), Professor Ian Fiarlamb (University of York), Professor Mohamed Mamlouk (Newcastle), Dr M. A. Carroll (Newcastle), Professor Elizabeth Gibson (Newcastle), Dr John Errington (Newcastle), Professor Richard A. Bourne (Leeds), Professor Tom W. Chamberlain (Leeds), Professor Christopher Hardacre (Manchester).

 

 

 

 

Publications