Department of Chemsitry

Professor M.L.H. Green

Inorganic Chemistry

malcolm.green@chem.ox.ac.uk

Telephone: 44 (0) 1865 275 917

Curriculum Vitae

 

Milestones in Original Research Contributions

The early days of research were in the field of synthesis and reactions of organotransition metal compounds and covered the period 1958– 2000.  In 1990 research commenced on heterogeneous catalysis and was focused towards hydrocarbon reactions. And in 1993 a completely new area of research into carbon nanotubes started.  The highlights of the discoveries made in these areas are listed below in chronological order. Key references are given in the text, often together with citation numbers presented as C. xxx (these were taken from the Web of Science on January 24th 2006). Those given in bold are particularly noteworthy.

Fundamental reactions of transition metal alkyl and carbene systems

The first demonstration of β-hydrogen abstraction from a metal-alkyl system, its reversibility, and its role as a model for the mechanism of metal catalysed olefin isomerisation. (12, 15, C. 186)   The reversible β-elimination reaction is widely available to transition metal alkyls with β -hydrogens.

The first demonstration of a reversible alpha-elimination of a metal-methyl giving a transition metal-methylene-hydride.(112 C. 97, 159 C. 109)  The reversible α-elimination reaction is widely available to  transition metal alkyls with α-hydrogens.

The first systematic synthesis of metallacyclobutanes and that their decomposition occurred with carbon-carbon bond cleavage, as previously proposed for the olefin metathesis reaction mechanism. (125 C. 111 129, C. 61, 133, C.  87)

The discovery of a general route to the synthesis of hydroxycarbene derivatives of transition metals: the second paper on transition metals carbene systems. (62 C. 107)

Pioneering studies of the activation of carbon-hydrogen G-H bonds in aromatic and aliphatic hydrocarbons by transition metal compounds

The first demonstrations for the intermolecular insertions of a transition metal centers into an aromatic C-H bonds and into saturated C-H aliphatic bonds. Both photochemical and thermal activation processes were used. (88 C. 78,  162 C.77, 259 C. 125)

The synthesis of the first zerovalent compounds of the early, refractory transition metal via the development of the electron-gun metal vapour synthesis experiment

The first demonstration of the electron gun furnace method for metal vapour synthesis, and its use for the synthesis of the first examples of zerovalent bis-eta-benzene compounds of titanium, zirconium, hafnium, niobium and tantalum. The synthesis of bis-benzenetungsten on a large scale (5-10 g) and many other metal atom reactions.(96 C. 67, 117 . 62, 186 C. 116, 255, 56, 171 C. 60, 234, C. 69)

Commercialization of equipment for Metal Vapour Synthesis by G.V. Planer Ltd.

Mechanisms

The formulation of general rules for the sterospecificity of nucleophilic addition to organometallic cations (with D.M.P. Mingos and S.G. Davies) (148 C. 298)

The formulation of a stimulating and accepted mechanism for Ziegler-Natta catalysed polymerisation of olefins. (156 C. 239)

The development of the field of organometallic solid state chemistry

There are several areas which essentially established this new field of research activity. (303, 305)

The synthesis of the first organometallic compound with a large second order non-linear optical behaviour. (286 C. 266)

The studies on synthesis and properties of organometallic intercalation compounds. (121, 143, 152, C.50, 160 ,282, 285, 290, 325, 351, 389, 398)

Studies on redox-active organometallic “soft salts”(287, 350)

There are now many active groups in this area. There were 53 recent articles cited under WoS search Organometallic Materials, the most highly cited of which was a review of organometallic non-linear optical materials (> 230 citations).

Pioneering studies on transition metal-hydrogen compounds

The first hydrides of tantalum and related tungsten and molybdenum compounds (with Wilkinson). (9, C.226)

The synthesis of the first stable nickel-hydride compounds – such systems had long been proposed following the discovery of nickel catalysed hydrogenation reactions by Paul Sabatier in 1913.(43) This work was one of the earliest demonstrations of the use of a bulky tertiary phosphine ligands to achieve increased thermal  stability, now a widely exploited strategy.

The development of M-H-C agostic bonds

The discovery of the agostic-ethyl and -methyl titanium compounds which  unambiguously demonstrated the  existence of the agostic M-H-C bond. (194, C.110, 216 C. 92, 251 C. 115)

There is now appreciation of the widespread role of agostic bonds as intermediates in many key metal-hydrocarbon reactions. (218 C. 68, 222 C. 1064, 302 C. 653)

A 2014 search for the word agostic using Web of Science gave 1,549 articles published by others using this term  since the concept “agostic bond” was proposed in 1983. (The word “agostic” has been selected for inclusion in the next edition of the Oxford English Dictionary. (222 C. 1064, 302  C. 653)

More Recent Research Programs

New Heterogeneous Catalysts for the Petrochemical and Green Energy Industries

The first catalyst for the selective Partial Oxidation of Methane to synthesis gas was discovered  in Oxford in 1990. (324 C. 341, 326 C. 160, 353 C. 266) This work attracted worldwide attention and many patents.  References to patents are listed in the Publications section below. A survey of the Web of Science showed that there have been 4628 articles under the search term “partial oxidation of methane” since the original report and that these publications came from >30 different countries.

The Oxford work also includes the discovery of the excellence of transition metal carbides as catalysts for hydrocarbon reforming reactions and Fischer-Tropsch Cataysts(472, 503, 511 C. 68, 520, 559, 563, 577, 587, 589, 632)

New carbide catalysts for hydrodesulphurisation have been discovered and patented. A superior catalyst for the oxidative removal of benzthiophenes from diesel has been identified and is being patented jointly with the company Saudi Aramco. Previously the Oxford Wolfson Catalysis Laboratory was set up in Oxford and has been supported for over 18 years by industrial collaborations.  These were with the Gas Research Institute, then CANMET Energy Technology Centre - Ottawa (CETC-Ottawa), the Wolfson Foundation and most recently with Saudi Aramco.

An exceptionally active, stable, and selective cobalt carbide catalyst for the conversion of synthesis gas to hydrocarbons (Fischer-Tropsch catalysis) was discovered in Oxford and patented. A spin-off company, originally called Oxford Catalysts Ltd, but has now changed to Velocys  (http://www.velocys.com) has been established to exploit the Fischer-Tropsch catalyst which produces gasoline and diesel from methane with greatly reduced sulphur content, as required by new legislation.  In 2012 British Airways announced  they will invest an estimate £500M over  eight years to develop a plant in London to convert London rubbish into jet fuels. This plant is now under construction and Velocys is  providing the equipment for the required conversion of syngas derived from the rubbish into the jet fuel  (http://www.velocys.com).

Pioneering studies on the chemistry of carbon nanotubes

This is the most recent new area of research.

It began with the discovery in Oxford of methods to open the ends  of  multi- and  single-walled carbon nanotubes and then their subsequent filling with many materials.  (Patent 415,  423 C. 461, 440 C. 71, 490 C.55, 496 C. 55, 523 C. 93, 587 C.79, 540 C. 114)

It has been shown that nano-crystals inside single wall carbon nanotubes (the worlds smallest crystals) have quite different properties from those of the bulk form of the filling material.  The exceptional number of citations gathered in a short period shows the interest in this work.  This programme was further supported by the British Government (EPSRC) by a £1,006,000 grant entitled “Molography”. This is a new concept whereby single wall carbon nanotubes are used to allow the determination of the relative atom positions of a single molecule in solution using modified transmission electron microscopy (with Professor A. Kirkland).

Most recently the use of wall-functionalized single wall carbon nanotubes filled with a radio isotope  of iodine has been shown to locate selectively in the lungs of  a mouse (with Benjamin Davis). This paper is highly cited (718).

The development of the Covalent Bond Classifiction (CBC) method.

The conception and proposal of a revolutionary approach to the classification of all covalent compounds of the elements. (444 C. 164) The ideas behind this work have a slowly but steadily received increasing acceptance and they are now taught to university students in many USA, UK and other countries.  The CBC method is now used and cited in well-known text books.  A recent CBC based  classification of two-electron three-centre bonds has attracted attention (with G Parkin and J.C. Green). (729)  An article to assist the teaching of the CBC method has recently appeared. (731) A website has been established to assist further expansion (http://www.covalentbondclass.org). 

Publications

All the above work is described in the 731 refereed papers given in the List of Publications and List of Patents. The total number of citations (May, 2014) is >30.000 and the h-factor is 81.

Please find linked a PDF containing a list Professor Green's 731 referred papers and list of patents.


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