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Geoffrey Wilkinson and Platinum Metals Chemistry by M Geoffrey Wilkinson and Platinum Metals Chemistry By M. L. H. Green University of Oxford, England and W. P. Griffith Imperial College of Science, Technology and Mrtlic.inr. London At this time, the second anniversar?,of Geoffrey WZkinson’s death on 26th September 1996, his work and influence on the development ojinorganic chemistry and the chemistry of the platinum group metals are recalled by two of his former students and colleagues. Geoffrey Wilkinson’.s early life and career, important areas of his platinurn metals research and work leading to the award in 1973 of the Nobel Prize are surveyed. He is remembered by his relationship with Johnson Matthex his work at Imperial College and by affectionute anecdotes,from the laboratory Professor Sir Geoffrey Wilkinson, F.R.S. (or of his ex-students came to work for it. On his Geoff as he was always called by his students twice-yearly visits to the Technology Centre in and colleagues) was one of the greatest inter- Sonning Common he would always take a plas- national post-war inorganic chemists; he made tic shopping bag filled with platinum metals remarkably original contributions to many areas residues, garnered from his research group and of transition metal chemistry, especially homo- from his colleagues - the used materials from geneous catalysis, organometallic and co-ordi- the loan scheme. nation chemistry. His research career, spanning On his retirement in 1988 to become Professor some 54 years, involved well over half of the ele- Emeritus, Johnson Matthey expressed their ments of the Periodic Table - he worked with appreciation of this mutually productive rela- almost every d-block transition metal, most of tionship by providing Geoff with the spacious the lanthanides and some of the actinides and Johnson Matthey laboratory at Imperial College. main group elements. Much of his work con- Here he continued very productive work with a cerned the six platinum group metals, and indeed small, creative team to the day before his death. many of his most important discoveries involved In 1964 Geoffrey Wilkinson wrote an article them. Ofhis 557 publications (l), well over one for Platinum Metals Review on platinum group third are concerned with the platinum metals. organometallic n-aromatic complexes (2). This article, however, preceded his important dis- The Johnson Matthey Connection coveries in the catalytic chemistry of these ele- The platinum metals Geoff used were invari- ments. As a fuller account of Geoff’s chemistry ably supplied by Johnson Matthey through the has already been published (l), this report will loan scheme (inaugurated in 1955 by his great focus on his life and work with the platinum friend, the late Frank Lever). This scheme has metals in the order of their interest to him, list- done much to foster university research in plat- ing items published in Platinum Metals Review. inum metals chemistry in the U.K. and over- seas. Over the years Geoff developed a close Early Life and Education connection with Johnson Matthey: not only were Geoffrey’s grandfather (also Geoffrey there the patents (involving for the most part Wilkinson) came to Todmorden, a small ‘cot- his rhodium catalysts) and consultancy, but also ton town’ in the West Riding of Yorkshire, close he had many kiends in the company - and some to Lancashire, from the Yorkshire town of Platinum Metals Rev., 1998, 42, (4), 168-173 168 Professor Sir Geoffrey Wilkinson 1921-1996 A Yorkshireman by birth, Geoffrey Wilkinson started his working life, during World War 11, on the atomic bomb project in Canada and then the United States. He returned to England in 1956 to the Sir Edward Frankland Chair of Inorganic Chemistry, at Imperial College in London. He was awarded the Nobel Prize for Chemistry in 1973 Boroughbridge. Geoffrey’s father, Harry, better taught. Geoff won a County Scholarship married Ruth Crowther, a weaver, and Geoffrey in 193 1 to Todmorden Secondary School (later was born on 14th July, 1921, the first of three Todmorden High School). A remarkable num- children, in the village of Springside on the ber of its pupils later became famous, including outskirts of Todmorden. Sir John Cockcroft, who worked with Rutherford In 1926 the family moved into Todmorden, at Cambridge and was to become, in 195 1, the which lies at the junction of three deep valleys first of the school’s two Nobel Laureates. Geoff in the heart of the Pennines, where the sur- made exceptional progress and in 1939 won a rounding moors rise 1000 feet above the town. Royal Scholarship to the Imperial College of The present population of 13,000 is about half Science and Technology, London University. that before the decline of the cotton industry, At Imperial his main subject was chemistry but there is still a strong local pride and sense but he also studied geology as an ancillary of community which Geoff shared all his life. subject, indeed in those early days he almost His eyes would light up when he spoke of “Tod” gave up chemistry in favour of geology. He or of the superb countryside close by. He often graduated in 1941 with a first class honours returned to the town to see friends and family, B.Sc. degree, the top student of his year, and and enjoyed walking and climbing in the area, went on to do a Ph.D. under H. V. A. Briscoe in the Lake District and the Yorkshire Dales. (at that time the only Professor of Inorganic Geoff‘s interest in chemistry began early. At Chemistry in the country) on “Some Physico- the age of six he was fascinated to see his father chemical Observations on Hydrolysis in the - a house painter and decorator - mixing his Homogeneous Vapour Phase”. This rather materials. His uncle managed a factory making Delphic title conceals the fact that the main sub- Epsom and Glauber’s salts in Todmorden, and strate studied was phosgene (Geoff later Geoff would recall how he loved to go on remarked that Briscoe “directed his Ph.D. Saturday mornings to tinker in the small labo- research from a safe distance”). ratory at the factory. Indeed, the family hoped In 1942 he was selected by the Joint Recruiting that he would eventually become its manager. Board as a scientific officer at the Atomic Energy His parents, like most people at that time, had project in Canada, and sailed to Halifax, Nova left full-time education by the age of 12 and they Scotia in January 1943. In Canada he worked were determined that their children should be at the University of Montreal and then at Chalk Platinum Metals Rev., 1998, 42, (4) 169 River, Ontario, on nuclear fission with many this day. Twenty years later Geoff wrote a vivid celebrated scientists -John Cockcroft (from his personal account of the discovery (4). From old school), Bertrand Goldschmidt, Charles 1952 to 1953 he made a number of other Coryell, Alfred Maddocks (later to go to bis(cyclopentadieny1) complexes, including those Cambridge), Jules Gueron and Pierre Auger of ruthenium, rhodium and iridium. During this being amongst them, and two scientists later period he used the fledgling technique of nuclear convicted of being spies for the Soviet Union, magnetic resonance (NMR) to show that cova- Alan Nunn May and Bruno Pontecorvo. lent metal hydrides (in this case Cp2ReH)gave After the war Geoff returned briefly to Britain high-field ‘H NMR shifts. This was crucial to and then went to the Lawrence Livermore his later work on rhodium hydrido complexes Laboratory at the University of California, and their catalytic properties. Berkeley, to work with Glenn T. Seaborg on the production of neutron-deficient isotopes of the Return to Imperial College transition elements and the lanthanides. It was In 1955 Geoff was appointed to Briscoe’s old said by Seaborg (and Geom that he made more chair at Imperial College ~ still the only estab- artificial isotopes - eighty nine - than anyone lished chair of inorganic chemistry in Britain - has ever made. From this time he started to and arrived there in January 1956. At 34 he was amass his vast knowledge of descriptive inor- one of the youngest professors that the College ganic chemistry, since in those days it was essen- has ever had, and here he did most of his plat- tial for nuclear chemists to have a profound inum metals work. It is tempting to trace this knowledge of the chemistry of the transition profound interest in platinum metals chemistry metals, the lanthanides and the actinides in order to his wartime and early peacetime radiochem- to devise appropriate means of separating and ical work, when he had made new radioisotopes identifying the products of nuclear fission reac- of rhodium and ruthenium. However, it is much tions. One of his nuclear transmutations was more likely that his fascination with these met- that of platinum into gold, which caught the als derived from his early experience and knowl- public imagination after a report in 1948 in the edge of their general chemistry, and in partic- ‘San Francisco Chronicle’ (“Scientist discovers ular with the remarkable versatility of oxidation gold mine in the cyclotron”). state changes exhibited by the metals, later In 1950 he went to M.I.T. and turned to co- harnessed for his catalytic work. ordination chemistry research. His first paper on this concerned the isolation of the unusual Rhodium Chemistry zerovalent complex, [Ni(PCl,),] (3). In 1951 he Geoff once said that much of his chemistry was appointed Assistant Professor of Chemistry concerned the ‘three Rs’ - rhodium, ruthenium at Harvard, and it was here that he did the and rhenium. At Berkeley, as part of his radio- research on ferrocene and other cyclopentadi- chemical work, he isolated the short-lived ‘%h, enyl compounds which was to lay the corner- one of the many fission products of ‘W, and stone of his Nobel Prize.
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