个人简介

I studied the structure of metal carbonyl fragments for my PhD under J. J. Turner. In that period in Cambridge and Newcastle from 1971-74, I established the existence of one of the first σ-complexes, Cr(CO)5(CH4), and the first metal-Xe bond, Cr(CO)5Xe, by photochemical matrix isolation. After periods in Muelheim, Edinburgh and Oxford, I moved to York in 1983 and was promoted to Professor of Chemistry in 1991. Along the route from Newcastle to York, I broadened my interests to encompass many aspects of the reaction mechanisms, photochemistry, spectroscopy and synthesis of organo-transition metal and metal hydride complexes. For instance, I have measured the rates of oxidative addition of H-H, C-H, B-H and S-H bonds at 4-coordinate Ru(0) centres and shown that oxidative addition of dihydrogen may occur with essentially no activation barrier. These studies required a combination of product investigation by solution NMR spectroscopy, nanosecond laser flash photolysis and matrix isolation. In recent work in this area, I have used photochemistry within the NMR probehead to observe manganese-propane complexes by NMR and am now developing laser pump-NMR probe methods with my colleague, Simon Duckett. Another major strand of my work has been the development of C-F bond activation at transition metals, culminating in new routes to metal fluoride complexes and fluoro-organics. One spin-off of this work has been the discovery that metal fluoride and metal hydride complexes can form halogen bonds to IC6F5. In turn, we have now been able to demonstrate that hydrogen bonds to neutral metal fluoride complexes are as strong as the strongest hydrogen bonds to organic acceptors. Throughout my work, I have collaborated with theorists to understand the wider implications of my experiments. Recent examples include comparisons of the selectivity for C-H versus C-F bond activation and the development of computational approaches to bond energy correlations. The theoretical predictions of the increase in metal carbon bond strength on ortho-fluorine substitution of a metal aryl have been vindicated by experiment.

研究领域

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Organometallic Photochemistry, Small Molecule Activation, Catalysis and Solar Fuels

Much of our research is concerned with homogeneous catalysis by transition metal complexes and the mechanisms that underlie it. Homogeneous catalysis has innumerable applications for synthesis of bulk chemicals on an industrial scale and for synthesis in the laboratory. Sometimes we probe active catalysts themselves, but often we probe individual steps in catalytic cycles through the use of dissociative photochemistry. Another recurring them of the research is small molecule activation: H-H, H-C, H-B, H-Si and especially C-F bonds are targets of interest. Supramolecular photochemistry targets the application of excited states of transition metal complexes for application in fluorescence sensing and in mimicking biological photosynthetic pathways. Often, electron transfer or charge separation follows on rapidly from light absorption. This photochemistry has great potential in the conversion of solar energy to chemical energy, also known as solar fuels. We belong to a research consortium called Solarcap that targets alkane oxidation and carbon dioxide reduction via solar cell. Our methodology ranges from conventional synthesis to laser spectroscopy, including NMR spectroscopy with laser photolysis within the probe and time-resolved spectroscopy on nanosecond and picosecond timescales. The group has very active links with computational chemists who help us study our reactions by quantum chemical methods. The research group is very international; we also have links to several other research groups in the UK and in other European countries.