Bernard Shaw conducted pioneering work on the chemistry of organotransition metal compounds, especially pi-allylic compounds and transition metal hydride complexes. He contributed greatly to our understanding of the bonding, stereochemistry, directional electronic effects, and mechanisms of reactions involved. He showed that transition metal complexes with bulky tertiary phosphine ligands have remarkable physical properties and unusual chemical and catalytic reactivity. The valuable concept of oxidative addition has been introduced for the synthesis of a wide range of complexes of platinum, iridium, or rhodium, and the first clear-cut examples provided of allylic bridges between two metal atoms. Subsequently, the chemistry of pi-allylic complexes has been extensively and usefully developed. He described the first carboxylate-bridged allylic-palladium and rhodium complexes, and these have since been much used in synthesis. He also made a major contribution to the chemistry of transition metal complexes, now often used or postulated as catalytic intermediates in hydrocarboxylation or hydrosilylation, for example, and in major industrial processes such as olefin isomerisation, hydroformylation, and homogeneous catalytic hydrogenation.
Professor Bernard Shaw FRS died on 8 November 2020.
Subject groups
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Chemistry
Chemistry, inorganic, Chemistry, organic
