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PROTAGONISTS IN CHEMISTRY
www.elsevier.com/locate/ica Inorganica Chimica Acta 331 (2002) xv – xvii
Volume dedicated to Professor A.G. Sykes
Professor A.G. Sykes FRS
This volume of Inorganica Chimica Acta is dedicated to Alfred Geoffrey (Geoff) Sykes. All those who know Geoff appreciate him as a good friend. To his students, and to the many postdoctoral workers who have passed through his lab, he is a teacher, a mentor and a loyal supporter. Geoff is a scientist who gives his time generously and who has inspired many young researchers in inorganic and bio-inorganic chemistry. Geoff Sykes was born in Huddersfield in 1934 and attended Huddersfield College, which was the local Grammar School. He obtained his B.Sc. in Chemistry from the University of Manchester in 1955, and went on to study for his Ph.D. (1958) under the supervision of Bill Higginson. Interestingly, Higginson was a Balliol College D.Phil student of R.P. Bell, and much of the thoroughness in Geoff’s kinetic work may well derive from this ‘family tree’ relationship. After his Ph.D., Geoff set out for a year of post-doctoral work in the USA at Princeton University (1958 –59). He then moved further afield to Australia and the University of Adelaide for a second year of postdoctoral studies (1959 – 60). At about this time (1960), Geoff’s first paper was published. The work was presented at the Faraday Society Discussion, organised by Professor Lord Wynne-Jones. This was held in Newcastle upon Tyne, a place Geoff was to become more familiar with at a later stage, when he took up a Chair at the University. The Meeting attracted a galaxy of physical kineticists, but also many associated with the newly emerging inorganic area including: – A. W. Adamson, F. Basolo, R.W. Dodson, J. Halpern, N. Hush, E.L. King, R.A. Marcus, L.E. Orgel, R.G. Pearson, D.R. Stranks, N. Sutin, H. Taube, R.J.P. Williams, and W.K. Wilmarth. The arrival of the sixties saw Geoff appointed to a Lectureship at the University of Leeds (1961). He was to remain at Leeds for some twenty years. The early sixties were productive and happy times both personally and professionally. In 1963 Geoff married Elizabeth (Liz), and they have three children – Richard, Andrew and Caroline. Liz has Elsevier Science B.V.
xvi
Protagonists in Chemistry
always been a tremendous help and support to Geoff, both in entertaining colleagues in their home, and also with secretarial work dealing with manuscripts and computing. On the scientific front Geoff’s early work progressed well. It is worth noting that five of his first seven pre-Leeds publications are single author papers (for various reasons, single author publications have become quite rare in chemistry, particularly so for young researchers). Four of these papers were on m-peroxo dicobalt(III) complexes. There was initially a strong reluctance to use the m-peroxo and m-superoxo terminology, and the superoxo ligand only gained full recognition in papers from around 1968 (J. Chem. Soc.). In 1964 as one of a series of monographs, Geoff completed a text on the Kinetics of Inorganic Reactions. These were early days for such a publication, but it sold well (2 prints) and helped to attract researchers to Leeds. Geoff will tell you that he probably benefited from the already well established Peter Sykes (unrelated!) name and books on Organic Mechanisms. The Sykes’ group of the late 1960’s and 1970’s thrived with recruitment of the best Leeds graduates, post-doctoral fellows, and many visiting scientists. This success in research was recognised with Geoff getting his Readership in 1970. In 1971, during a first lecture tour to Europe, Geoff met Karl Wieghardt (then in Heidelberg) who also had an interest in dicobalt(III) complexes. This led to Karl spending a year in Leeds, in what proved to be a wonderfully productive year. In 1973, while still at Leeds, Geoff was awarded his D.Sc. from the University of Manchester, clearly confirming the quality of his research. Many other, now well established, scientists spent time with Geoff in Leeds. Those included: Yoichi Sasaki (now Hokkaido), Andrea Bakac (Ames, Iowa), Takashi Shibahara (Okayama), Ramasami (Madras), David Weatherburn (Wellington), Graham Lappin (Notre Dame), Richard Henderson (Geoff’s successor to the Chair of Inorganic Chemistry at Newcastle), and Ph.D. students Roger Thorneley (Norwich) and Fraser Armstrong (Oxford). Geoff’s main research interest while at Leeds was in Inorganic Reaction Mechanisms. Early work in Leeds (already alluded to above) included studies on redox and substitution reactions of binuclear cobalt complexes. Other work provided a major impact in the understanding of inner- and outer-sphere redox reactions. Rate laws with numerator and denominator terms were a speciality! Geoff also made important contributions to the area of Mo and W aqueous chemistry. In addition to this ‘mainstream’ inorganic work, Geoff developed an increasing interest in biological inorganic chemistry. Work on plastocyanin (Segal) and the ferredoxins (Armstrong) can be traced back to around 1977 whilst he was still in Leeds, with encouragement and help from Peter Knowles, Ralph Wilkins (Nato Fellowship) and Hans Freeman (Sydney, British Council Exchange). In 1980 Geoff was appointed to the Established Chair of Inorganic Chemistry in Newcastle, there to join Professors Sir James Baddiley (Organic) and David Whiffen (Physical) both FRS. In Newcastle (with Richens and Castilla-Blum) studies on the aqueous chemistry of iridium continued, but inorganic studies soon became focussed almost entirely on Mo and W aqua ions, and extensive work on the chalcogenide clusters followed – still on-going. The six coordination of Mo (and W) in the chalcogenide clusters giving e.g. [Mo4S4(H2O)12]4 + provides an interesting contrast with the tetrahedral coordination observed for the ferrodoxins e.g. [Fe4S4L4]. Long term (\ 10 years) and highly successful collaborations with the Russian Academy of Sciences, Institute of Inorganic Chemistry in Novosibirsk (Fedin, Sokolov), and the University of La Laguna in Tenerife (Mederos, Hernandez-Molina) were extensively supported by European Research Grants since 1990. There have also been very productive exchanges with the kinetics group at the University of Bloemfontein (Leipoldt, Lamprecht, Roodt, Swarts), and the inorganic groups at Stellenbosch (Cruywagen, Koch). The move to Newcastle provided the opportunity to extend the metalloprotein studies which really took off. In and around 1984–5 New Blood lectureships were a feature of the UK scene – some 35 in Inorganic Chemistry. Openings in inorganic biochemistry (Edinburgh) and inorganic aqueous solutions studies (Stirling) were taken up by Steve Chapman (first Newcastle Ph.D.) and Dave Richens. Dave, now at St. Andrews, has recently (1997) produced an encyclopaedic 592 page book on the chemistry of aqua ions (Wiley), which has been well received. Meanwhile work on blue Cu proteins (notably McGuinnis, Dennison, Kyritsus) and the ferrodoxins (Im, Worrall) continued, and the attachment of [Ru(NH3)5H2O)]2 + to surface histidine residues provided an opportunity for studying intramolecular electron transfer from the attached RuII (Jackman, Lloyd-Raven). Recently studies on plastocyanin were very nicely rounded off by flash photolysis studies on a [Ru(terpy)(bipy)H2O]2 + derivative (JACS, 1998). Mechanistic studies on hemerythrin (Graeme Armstrong), hemocyanin (Colin Andrew), aconitase (Faridoon, Zhuang), and the binuclear Fe-enzymes ribonucleotide reductase (Han, Dobbing), and purple acid phosphatase (Aquino, Twitchett) have also provided important insights. A feature of the galactose oxidase (GO) studies were the meetings with the Leeds group (Knowles, Phillips and McPherson). As in the case of ribonucleotide reductase, GO has a tyrosyl free radical redox component. The substrate binding site on the Cu provides an excellent system for kinetic and thermodynamic studies. The studies provide a good example of the use of quantitative solution studies, using techniques which in some laboratories seem to have become something of a lost art! The Newcastle team for .
Protagonists in Chemistry
xvii
these studies was made up of three Ph.D. students, Saysell, Borman and Wright (top firsts in their respective years), and post-doctoral fellows Sokolowski and Twitchett. Geoff’s group has produced 53 Ph.Ds, and has hosted greater numbers of both post-doctoral fellows and visitors. Over 40 different nationalities have spent time with the group (most recently from Kazakhstan and Chile), and helped provide a friendly and productive atmosphere for research. The group has 470 publications, Geoff has edited 28 books, most of which have been in the high profile Advances in Inorganic Chemistry series (Vol. 32–53). Collaborations with Dr. G.A. Salmon using (pulse radiolysis) at the University of Leeds, and with Professors Clegg (X-ray structures), and McFarlane (NMR) at the University of Newcastle have featured prominently. Travel, it seems, has always featured high on Geoff’s list of interests (post-doctoral studies led to 6 months of foreign travel!), and he has always thrived on the many appointments to Visiting Positions. These have included visits to: – 1968 Argonne National Laboratories, USA; 1975 Heidelberg Univ., 1977 Leoben Univ., Austria, 1978 Northwestern Univ., USA, 1981 Univ of Berne, Switzerland, 1981 Denmark and Sweden, 1984 Univ. of Sydney, 1986 JSPS Fellow, Japan, 1989 Univ. of Kuwait, 1992 Univ of Adelaide, 1992 Univ of Melbourne, 1995 Memorial Univ., Newfoundland, 1997 Univ of West Indies, (Barbados, Trinidad, Jamaica) 1998 Univ of Lausanne, Switzerland, 1999 Stellenbosch and Bloemfontein, South Africa, 2000 Univ of La Laguna, Spain, 2001 City University, Hong Kong,. He has never taken a sabbatical leave. In 1999 he was elected Fellow of the Royal Society for mechanistic studies on inorganic biochemistry (metalloprotein) and inorganic coordination complexes, possibly the first in this area. While in Leeds he organised the first of the RSC Inorganic Discussion Group Meetings, and became Secretary and then Chairman of the group. In 1985 he organised one of the Climax/Amax Molybdenum Conferences, and in 1992 the first European Bioinorganic Conference (Eurobic), both in Newcastle. In September 1995 ex-students and members of his group, in particular Fraser Armstrong, organised a celebration of Geoff’s 60th birthday at St John’s College Oxford, a very pleasant and memorable occasion. It is a great pleasure for me to have participated in the preparation of this special issue of contributions from friends and former colleagues in honour of Geoff, and to help summarise his contributions to inorganic chemistry in this way. Many others from his group have of course contributed extensively to the various areas indicated. Those that have contributed to this volume and many more will, I’m sure, want to wish him an enjoyable and happy retirement. November 30th 2001 Stephen K. Chapman Department of Chemistry University of Edinburgh UK
.
Volume dedicated to Professor A.G. Sykes
Professor A.G. Sykes FRS
This volume of Inorganica Chimica Acta is dedicated to Alfred Geoffrey (Geoff) Sykes. All those who know Geoff appreciate him as a good friend. To his students, and to the many postdoctoral workers who have passed through his lab, he is a teacher, a mentor and a loyal supporter. Geoff is a scientist who gives his time generously and who has inspired many young researchers in inorganic and bio-inorganic chemistry. Geoff Sykes was born in Huddersfield in 1934 and attended Huddersfield College, which was the local Grammar School. He obtained his B.Sc. in Chemistry from the University of Manchester in 1955, and went on to study for his Ph.D. (1958) under the supervision of Bill Higginson. Interestingly, Higginson was a Balliol College D.Phil student of R.P. Bell, and much of the thoroughness in Geoff’s kinetic work may well derive from this ‘family tree’ relationship. After his Ph.D., Geoff set out for a year of post-doctoral work in the USA at Princeton University (1958 –59). He then moved further afield to Australia and the University of Adelaide for a second year of postdoctoral studies (1959 – 60). At about this time (1960), Geoff’s first paper was published. The work was presented at the Faraday Society Discussion, organised by Professor Lord Wynne-Jones. This was held in Newcastle upon Tyne, a place Geoff was to become more familiar with at a later stage, when he took up a Chair at the University. The Meeting attracted a galaxy of physical kineticists, but also many associated with the newly emerging inorganic area including: – A. W. Adamson, F. Basolo, R.W. Dodson, J. Halpern, N. Hush, E.L. King, R.A. Marcus, L.E. Orgel, R.G. Pearson, D.R. Stranks, N. Sutin, H. Taube, R.J.P. Williams, and W.K. Wilmarth. The arrival of the sixties saw Geoff appointed to a Lectureship at the University of Leeds (1961). He was to remain at Leeds for some twenty years. The early sixties were productive and happy times both personally and professionally. In 1963 Geoff married Elizabeth (Liz), and they have three children – Richard, Andrew and Caroline. Liz has Elsevier Science B.V.
xvi
Protagonists in Chemistry
always been a tremendous help and support to Geoff, both in entertaining colleagues in their home, and also with secretarial work dealing with manuscripts and computing. On the scientific front Geoff’s early work progressed well. It is worth noting that five of his first seven pre-Leeds publications are single author papers (for various reasons, single author publications have become quite rare in chemistry, particularly so for young researchers). Four of these papers were on m-peroxo dicobalt(III) complexes. There was initially a strong reluctance to use the m-peroxo and m-superoxo terminology, and the superoxo ligand only gained full recognition in papers from around 1968 (J. Chem. Soc.). In 1964 as one of a series of monographs, Geoff completed a text on the Kinetics of Inorganic Reactions. These were early days for such a publication, but it sold well (2 prints) and helped to attract researchers to Leeds. Geoff will tell you that he probably benefited from the already well established Peter Sykes (unrelated!) name and books on Organic Mechanisms. The Sykes’ group of the late 1960’s and 1970’s thrived with recruitment of the best Leeds graduates, post-doctoral fellows, and many visiting scientists. This success in research was recognised with Geoff getting his Readership in 1970. In 1971, during a first lecture tour to Europe, Geoff met Karl Wieghardt (then in Heidelberg) who also had an interest in dicobalt(III) complexes. This led to Karl spending a year in Leeds, in what proved to be a wonderfully productive year. In 1973, while still at Leeds, Geoff was awarded his D.Sc. from the University of Manchester, clearly confirming the quality of his research. Many other, now well established, scientists spent time with Geoff in Leeds. Those included: Yoichi Sasaki (now Hokkaido), Andrea Bakac (Ames, Iowa), Takashi Shibahara (Okayama), Ramasami (Madras), David Weatherburn (Wellington), Graham Lappin (Notre Dame), Richard Henderson (Geoff’s successor to the Chair of Inorganic Chemistry at Newcastle), and Ph.D. students Roger Thorneley (Norwich) and Fraser Armstrong (Oxford). Geoff’s main research interest while at Leeds was in Inorganic Reaction Mechanisms. Early work in Leeds (already alluded to above) included studies on redox and substitution reactions of binuclear cobalt complexes. Other work provided a major impact in the understanding of inner- and outer-sphere redox reactions. Rate laws with numerator and denominator terms were a speciality! Geoff also made important contributions to the area of Mo and W aqueous chemistry. In addition to this ‘mainstream’ inorganic work, Geoff developed an increasing interest in biological inorganic chemistry. Work on plastocyanin (Segal) and the ferredoxins (Armstrong) can be traced back to around 1977 whilst he was still in Leeds, with encouragement and help from Peter Knowles, Ralph Wilkins (Nato Fellowship) and Hans Freeman (Sydney, British Council Exchange). In 1980 Geoff was appointed to the Established Chair of Inorganic Chemistry in Newcastle, there to join Professors Sir James Baddiley (Organic) and David Whiffen (Physical) both FRS. In Newcastle (with Richens and Castilla-Blum) studies on the aqueous chemistry of iridium continued, but inorganic studies soon became focussed almost entirely on Mo and W aqua ions, and extensive work on the chalcogenide clusters followed – still on-going. The six coordination of Mo (and W) in the chalcogenide clusters giving e.g. [Mo4S4(H2O)12]4 + provides an interesting contrast with the tetrahedral coordination observed for the ferrodoxins e.g. [Fe4S4L4]. Long term (\ 10 years) and highly successful collaborations with the Russian Academy of Sciences, Institute of Inorganic Chemistry in Novosibirsk (Fedin, Sokolov), and the University of La Laguna in Tenerife (Mederos, Hernandez-Molina) were extensively supported by European Research Grants since 1990. There have also been very productive exchanges with the kinetics group at the University of Bloemfontein (Leipoldt, Lamprecht, Roodt, Swarts), and the inorganic groups at Stellenbosch (Cruywagen, Koch). The move to Newcastle provided the opportunity to extend the metalloprotein studies which really took off. In and around 1984–5 New Blood lectureships were a feature of the UK scene – some 35 in Inorganic Chemistry. Openings in inorganic biochemistry (Edinburgh) and inorganic aqueous solutions studies (Stirling) were taken up by Steve Chapman (first Newcastle Ph.D.) and Dave Richens. Dave, now at St. Andrews, has recently (1997) produced an encyclopaedic 592 page book on the chemistry of aqua ions (Wiley), which has been well received. Meanwhile work on blue Cu proteins (notably McGuinnis, Dennison, Kyritsus) and the ferrodoxins (Im, Worrall) continued, and the attachment of [Ru(NH3)5H2O)]2 + to surface histidine residues provided an opportunity for studying intramolecular electron transfer from the attached RuII (Jackman, Lloyd-Raven). Recently studies on plastocyanin were very nicely rounded off by flash photolysis studies on a [Ru(terpy)(bipy)H2O]2 + derivative (JACS, 1998). Mechanistic studies on hemerythrin (Graeme Armstrong), hemocyanin (Colin Andrew), aconitase (Faridoon, Zhuang), and the binuclear Fe-enzymes ribonucleotide reductase (Han, Dobbing), and purple acid phosphatase (Aquino, Twitchett) have also provided important insights. A feature of the galactose oxidase (GO) studies were the meetings with the Leeds group (Knowles, Phillips and McPherson). As in the case of ribonucleotide reductase, GO has a tyrosyl free radical redox component. The substrate binding site on the Cu provides an excellent system for kinetic and thermodynamic studies. The studies provide a good example of the use of quantitative solution studies, using techniques which in some laboratories seem to have become something of a lost art! The Newcastle team for .
Protagonists in Chemistry
xvii
these studies was made up of three Ph.D. students, Saysell, Borman and Wright (top firsts in their respective years), and post-doctoral fellows Sokolowski and Twitchett. Geoff’s group has produced 53 Ph.Ds, and has hosted greater numbers of both post-doctoral fellows and visitors. Over 40 different nationalities have spent time with the group (most recently from Kazakhstan and Chile), and helped provide a friendly and productive atmosphere for research. The group has 470 publications, Geoff has edited 28 books, most of which have been in the high profile Advances in Inorganic Chemistry series (Vol. 32–53). Collaborations with Dr. G.A. Salmon using (pulse radiolysis) at the University of Leeds, and with Professors Clegg (X-ray structures), and McFarlane (NMR) at the University of Newcastle have featured prominently. Travel, it seems, has always featured high on Geoff’s list of interests (post-doctoral studies led to 6 months of foreign travel!), and he has always thrived on the many appointments to Visiting Positions. These have included visits to: – 1968 Argonne National Laboratories, USA; 1975 Heidelberg Univ., 1977 Leoben Univ., Austria, 1978 Northwestern Univ., USA, 1981 Univ of Berne, Switzerland, 1981 Denmark and Sweden, 1984 Univ. of Sydney, 1986 JSPS Fellow, Japan, 1989 Univ. of Kuwait, 1992 Univ of Adelaide, 1992 Univ of Melbourne, 1995 Memorial Univ., Newfoundland, 1997 Univ of West Indies, (Barbados, Trinidad, Jamaica) 1998 Univ of Lausanne, Switzerland, 1999 Stellenbosch and Bloemfontein, South Africa, 2000 Univ of La Laguna, Spain, 2001 City University, Hong Kong,. He has never taken a sabbatical leave. In 1999 he was elected Fellow of the Royal Society for mechanistic studies on inorganic biochemistry (metalloprotein) and inorganic coordination complexes, possibly the first in this area. While in Leeds he organised the first of the RSC Inorganic Discussion Group Meetings, and became Secretary and then Chairman of the group. In 1985 he organised one of the Climax/Amax Molybdenum Conferences, and in 1992 the first European Bioinorganic Conference (Eurobic), both in Newcastle. In September 1995 ex-students and members of his group, in particular Fraser Armstrong, organised a celebration of Geoff’s 60th birthday at St John’s College Oxford, a very pleasant and memorable occasion. It is a great pleasure for me to have participated in the preparation of this special issue of contributions from friends and former colleagues in honour of Geoff, and to help summarise his contributions to inorganic chemistry in this way. Many others from his group have of course contributed extensively to the various areas indicated. Those that have contributed to this volume and many more will, I’m sure, want to wish him an enjoyable and happy retirement. November 30th 2001 Stephen K. Chapman Department of Chemistry University of Edinburgh UK
.