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Johnson Matthey Technol. Rev., 2021, 65, (1), 4

doi:10.1595/205651320x15864407040160

Professor Robert D. Gillard: Transition Metal Chemist 1936–2013: Part I

From early life to the University of Kent at Canterbury

  • John Burgess
  • Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
  • Martyn V. Twigg*
  • Twigg Scientific & Technical Ltd, Caxton, Cambridge CB23 3PQ, UK
  • *Correspondence may be sent via the Editorial Team: tech.review@matthey.com
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Article Synopsis

This first part of a two-part commemoration of the life and work of Robert D. Gillard begins with a biographical outline which provides a context for his chemical achievements. He was awarded a State Scholarship and after his National Service in the Royal Air Force he went up to St Edmund Hall, Oxford, to read Chemistry. There follows a chronological account of his career in Chemistry starting with his undergraduate days in Oxford, where a Part II project with Dr Harry Irving on alkaline earth and cobalt complexes proved seminal. His PhD research at Imperial College, London in the Geoffrey Wilkinson group broadened his experience into the then poorly developed chemistry of rhodium and other platinum group metal complexes. Gillard next went to Sheffield University as a Lecturer where he developed independent research while continuing to work on earlier topics. There followed a move to Canterbury as a Reader at the University of Kent. In his particularly productive seven years there with a large research group he widened his experience further, expanding his interests in such areas as the optical properties of transition metal complexes, considering biological and medical relevance, and increasing the range of metals and ligands he investigated. His subsequent time at Cardiff and then into retirement will be covered in the second part of this commemoration.

1. Introduction

With the death of Professor Robert D. Gillard on 4th June 2013 in Cardiff, UK, Chemistry lost one of its more charismatic and energetic figures whose work on transition metal coordination complexes and particularly chiral metal complexes spanned more than four decades. His chemical research began with a student Part II Project at the University of Oxford supervised by Dr H. M. N. H. Irving on the formation of optically active and racemic isomers of 1,2-propanediamine tetraacetate (pdta) complexes with alkaline earth metals. In his typical fashion, Gillard expanded greatly the scope of the project to include transition metal complexes. This experience kindled a life-long interest in the optical activity of metal complexes and inorganic coordination chemistry in general. He developed a particular interest in compounds and complexes of the platinum group metals (pgms), publishing substantial amounts of research on rhodium (over 60 articles) and platinum (over 30 articles), with smaller contributions on ruthenium and iridium complexes (12 and 9 articles respectively). He thus made a significant contribution to the renascence of interest in these elements at the time.

The present article provides some biographical background before Gillard’s published research contributions are reviewed selectively in chronological order. After leaving Oxford and following a short break from academia Gillard worked for a PhD (1961–1964) with Geoffrey Wilkinson at Imperial College, London. He then went to the University of Sheffield as a Lecturer (1964–1966) after which he moved to the University of Kent at Canterbury as a Reader (1966–1973). Gillard then moved to Cardiff University to take the Chair in Inorganic Chemistry. The second part of this commemoration covers his time there and his work into retirement.

2. Biographical and General Background

2.1 Parents, Schools and Military Service

Robert David Gillard was born on 23rd August 1936 in Balham in the London Borough of Wandsworth. His mother, Eva Margery Gillard (née Arthur 1914–1985) and father (who at the time was a bus conductor for London Transport) were married in Wandsworth in 1933. Gillard’s father Thomas Gillard (1904–1983), who referred to himself as Thomas Patrick Gillard, was born in Nottingham and the family moved to Bradford where in 1911 his sister Elizabeth was born. Gillard’s grandfather, also Thomas Gillard, was born in 1873 in Newcastle-under-Lyme where he worked in iron works there. Gillard’s older brother, Thomas R. Gillard, was also born in South London. Gillard did well at school and he won a Surrey County Council scholarship to Mitcham Grammar School where he gained distinctions in all his O-level and in four A-level examinations. He won a State Scholarship in Pure Mathematics to Oxford University but before going up to Oxford he did National Service in the Royal Air Force (1954–1956), becoming a Pilot Officer. Part of his training was undertaken in Canada. Much later he told stories illustrating his navigation skills were not always perfect. For instance, he once said (as related to MVT by Dr J. G. Jones in 2015) that when flying from Libya to Malta his plane overshot and landed in Cyprus! After his time in the RAF Gillard went up to Oxford University for his undergraduate studies, not for Pure Mathematics but rather to read Chemistry and the reasons for this change are unclear to the present authors.

2.2 The Oxford Years (1956–1960)

On leaving the RAF Gillard started undergraduate studies at St Edmund Hall in Oxford, where his elder brother had been earlier. His headmaster at Mitcham Grammar School (Mr G. I. P. Courtney) in a letter to St Edmund Hall said

“I have made it my business to observe Gillard in various activities. He does essays for me which are thoughtful and cogent. From my conversations with him I know that he reads widely and with zest. He takes, of course, a very full part in school life – plays for the first XV, the second XI, and swims for the school. He works hard in the school choir and has taken leading parts in the school opera production. He would have been in the cast of this term’s Shaw production if it had not clashed with the date of the examination”

He went on to say

“Gillard is a joint Vice-Captain of the school. He was a strong candidate for the Captaincy, but I finally chose a boy who was a year his senior. As a Prefect he is loyal and co-operative.”

It is not clear why Gillard studied Chemistry rather than Pure Mathematics at Oxford, perhaps he had developed a strong interest in the subject towards the end of his time at school? At first, as in the Royal Air Force, he participated in sport activities and for a while he represented St Edmund Hall at rugby and rowing in his first year (1956–1957). He rowed in the 5th VIII, in seat 5, and he also led a particularly active social life. However, these activities had to be curtailed as he only managed to obtain a minimal Pass in the Chemistry Part I examinations in the School of Natural Science, and increasing academic demands led to St Edmunds Hall’s Principal writing on 3rd June 1957 to Surrey County Council, the Ministry of Education, and Gillard’s parents about him being seriously in dereliction of his studies and, unless there was “an improvement by the end of this term we shall be obliged to discontinue his residence. But even by 27th June 1957 the Principal was able to write to the Ministry of Education (who were funding his State Scholarship) stating

“since the warning I gave him about the middle of term, there has been a marked improvement in Mr Gillard’s work. His attendances at the laboratory are reported to be the best of all the students in his year, and in other respects he appears to be working quite satisfactorily. In view of this I am not proposing to take any further action beyond warning him that this improvement must be maintained.”

Clearly Gillard maintained his improved academic standing and in 1960 he was awarded his BA with First Class honours. His subsequent Part II research project was supervised by Dr Harry Irving (14). His project began with the formation of optically active and racemic isomers of pdta complexes with alkaline earth cations and highlighted to Gillard the chirality some metal complexes can have. Gillard expanded the project to include transition metals, and collaboration with Irving in this area continued over almost a decade and resulted in several joint publications. His BSc thesis was entitled ‘Conformational Factors and the Stability of Some Metal Complexes’; his BSc was awarded in September 1961 (Figure 1). This research experience strongly influenced the directions of much of his subsequent academic work.

Fig. 1

Graduation photograph of Robert D. Gillard at the University of Oxford. He completed his Part II research project with Dr Irving in 1961 and was duly awarded his BSc (Courtesy of Isabelle Gillard and Fiona Hammett)

Graduation photograph of Robert D. Gillard at the University of Oxford. He completed his Part II research project with Dr Irving in 1961 and was duly awarded his BSc (Courtesy of Isabelle Gillard and Fiona Hammett)

Gillard had indeed done very well at Oxford and on 13th July 1960 the St Edmund Hall Principal wrote to him saying

“I was delighted to hear that you had obtained a First. This is a splendid achievement and it does you every credit. I know that at times your tutor thought you might not manage to pull it off, but you have confounded your critics in a manner which must be really satisfying and pleasant to look back upon.”

Gillard did not look back – he moved forward with vigour!

In 1957, while an undergraduate at Oxford, Gillard met Diane Laslett, a trainee nurse at Hammersmith Hospital, at the Hurlingham Club in London through a mutual friend (who happened to be at Imperial College). Later that year they were married at St Luke’s Church in Ramsgate, on 28th December. They had three children: Isabelle born in 1958 in Oxford, Andrew born in 1964 in Kent and Duncan born in 1966 in Sheffield. Tragically Duncan was killed in a car crash in Devon in 1998. Isabelle studied Law at the University of Birmingham and has a very successful career as a lawyer, while her brother Andrew studied mathematics at University College London and later worked in digital information technology areas.

2.3 The Commercial Year (1960–1961)

After leaving Oxford Gillard joined the Agricultural Department of Burt, Boulton and Haywood Ltd at Belvedere in Kent as a European Liaison Chemist. Burt, Boulton and Haywood Ltd (BBH) was the oldest timber preservation company in the world, established in 1848. By the time Gillard joined the business they were importing pine for their major activity, making and treating wooden telephone and electricity poles, from Iivari Mononen in Finland. The Iivari Mononen Group eventually absorbed BBH, whose pole and fence post treatment operations are now based in Newport, South Wales. Gillard found work in industry tedious and frustrating, so wanted to go back into academia. This return was soon accomplished, in a manner determined by a coincidental turn of events.

2.4 Imperial College and Sheffield University (1961–1966)

Unknown to Gillard Professor Irving, who had left Oxford and taken a chair at Leeds University, wrote to him offering him a place to do a PhD at Leeds. But the offer letter did not reach Gillard for some time because his address had changed. By the time Irving’s letter reached Gillard he had secured a position with Professor Geoffrey Wilkinson (5, 6) to work for a PhD at Imperial College supported by being an Assistant Lecturer, and later a Lecturer.

This came about serendipitously by talking with an acquaintance, Dr Ron Ashby, who was a Senior Lecturer in Engineering at Imperial College. He arranged for Gillard to meet Dr A. J. E. Welch, an inorganic chemist at Imperial College who was involved in editing later editions of the important Thorpe’s Dictionary of Applied Chemistry”. Welch introduced Gillard to Professor Geoffrey Wilkinson who there and then offered him an Assistant Lecturer position; he also registered for a PhD supervised by Wilkinson! It appears Wilkinson’s haste was caused by Tony Poë (7, 8), who had a similar position to that offered to Gillard, leaving Imperial College to spend a year in America at North Western University at Evanston in Illinois.

Gillard started at Imperial College in late 1961 and in 1963 he was promoted to Lecturer. In 1964 he was awarded a PhD degree with a thesis entitled Spectroscopic Studies of Transition Metal Compounds’ (9, 10). During this period Gillard worked industriously, mainly at preparing and characterising rhodium(III) complexes that are usually kinetically inert although their reactions and preparation can often be catalysed by the presence of small amounts of more reactive reduced rhodium species that can often be conveniently produced via reaction with a small amount of ethanol. After completing his PhD Gillard moved to the University of Sheffield as a Lecturer in Chemistry. For two years Gillard prepared and delivered chemistry lectures at the University of Sheffield, continued research and maintained his prolific publication rate of research papers. Some of his papers at this time were based on work done or started at Imperial College and also extensions to some of his Oxford research involving collaboration with H. M. N. H. Irving. Research was also initiated with postgraduate students at Sheffield.

Gillard said his first PhD student was J. H. Dunlop, who had worked with him at Imperial College and then moved to Sheffield with him (11). Other PhD students rapidly followed. At Sheffield these included Nicholas C. Payne and Keith Garbett. They were followed by increasing numbers of graduate students and postdoctoral workers later at Canterbury and then at Cardiff, and perhaps there were a hundred in all throughout his career.

In 1966 Gillard’s prolific research output was recognised by the award of the Chemical Society’s Meldola Medal for 1965 for having “conducted the most meritorious and promising original investigations in chemistry and published the results of those investigations”.

2.5 Canterbury and Cardiff (1966–2013)

In the year following the award of the Meldola Medal, Gillard (1966) was promoted to Reader in Chemistry at the recently established (1965) University of Kent at Canterbury (Figure 2). This provided opportunities for considerably enlarging his Research Group, facilitated in 1967 by the founding of the Medical Research Council Research Group on Biological Inorganic Chemistry, of which he was Director until 1975. This brought into his Group people skilled in bio-techniques who studied the effects of inorganic species on biological systems, though they never looked at interactions, for example of platinum or rhodium complexes with DNA, at the molecular level.

Fig. 2

Photograph of Robert D. Gillard just after he arrived at the University of Kent at Canterbury in 1966 (Courtesy of Tony Fassom)

Photograph of Robert D. Gillard just after he arrived at the University of Kent at Canterbury in 1966 (Courtesy of Tony Fassom)

Gillard’s time at Canterbury was very productive with about 100 published papers during his time there (some 15 per year) although this was rather less than the halcyon years at Imperial College and the University of Sheffield (more than 20 papers were published in 1966). However, the period at Canterbury was brought to a close in 1973 by a move to the Chair of Inorganic Chemistry at the now University of Cardiff. Sometime later the Department of Chemistry at Canterbury closed (1990 – albeit to be re-opened several years later), and one can but wonder what might have happened had Gillard’s successful dynamism been retained at Canterbury by him being appointed to a Chair there rather than him having to seek promotion elsewhere.

As Professor of Inorganic Chemistry at Cardiff Gillard’s chemical interests broadened and included a continued fascination with the potential hydration of C=N bonds in diimine ligands activated by coordination to metal centres by analogy with the reactions of some alkylated aromatic nitrogen organic compounds. He published widely on this topic that was generally referred to as ‘covalent hydration’. His interests also extended into several new areas including geological inorganic chemistry, and a copper nickel hydroxyl chloride mineral (Cu3NiCl2(OH)6) discovered in Western Australia was named ‘Gillardite’ after him by his former colleague at Cardiff, Peter Williams, in recognition of his contributions to inorganic chemistry (Figure 3) (12).

Fig. 3

Gillardite, Cu3NiCl2(OH)6, a mineral from the 132 North deposit, Widgiemooltha, Western Australia named in 2007 (see (12)). Its zinc analogue is Herbertsmithite also from Widgiemooltha

Gillardite, Cu3NiCl2(OH)6, a mineral from the 132 North deposit, Widgiemooltha, Western Australia named in 2007 (see (12)). Its zinc analogue is Herbertsmithite also from Widgiemooltha

Music had an important role in Gillard’s life. He played the piano and was a good oboe player, continuing lessons in Canterbury, and it is said he played semi-professionally when visiting the University of Minnesota. During his school days he enjoyed singing – he had parts in some school operas. At school and later in life he sang in several choirs. When in Cardiff Gillard took great delight in being a member of the Second Tenors section in the long-established Cwmbach Male Voice Choir. The choir’s history, printed in 2001, covered the years of the choir’s existence from 1921 to 2001 and shows on average there were around 12 concerts a year between 1970 and 2000. Gillard sang in the choir for almost 20 years (July 1976–1995). The choir visited many towns and cities around the UK, and sang memorably at several chemistry conferences. During this period the choir was successful in several competitions, winning prizes in Wales and Ireland, and had considerable success in the Bela Bartok Choral Festival in Hungary in 1986. Gillard apparently was present on the tour of Hungary which followed this competition.

While at Cardiff Gillard married his second wife Anne Howard in Leicester in 1982. His Best Man was Malcolm Pilbrow, who had been one of his research students at Canterbury and was co-author of several publications on platinum complexes between 1969 and 1984. Anne had worked for the Royal Society of Chemistry organising various conferences and events. They had two children, Fiona born in 1983 and Thomas born in 1985 both in South Glamorgan. Later Fiona studied law at Oxford University and became a lawyer. Her brother Thomas works in the construction design industry in London.

Gillard’s retirement from the Chair of Inorganic Chemistry at Cardiff in 1998 was impelled by ill health and he underwent successful triple bypass heart surgery. However, complications resulting from his Type 2 diabetes condition eventually led to serious health problems, especially those associated with kidney function. Ultimately renal failure coupled with a stroke led to his death in June 2013.

2.6 Travel and Collaborations

Gillard had an enthusiastic lecturing style, possibly influenced by that of his PhD supervisor Geoffrey Wilkinson at Imperial College, and throughout his academic career he travelled and lectured widely. He established many professional friendships around the world that often stimulated new directions for his research. For instance, in 1966 he spent the summer in Italy in the laboratory of Professor Lamberto Malatesta in Milan. During 1971 he was a Visiting Professor at the University of Minnesota in the USA, and there he consulted with the 3M Company in St Paul, a relationship that continued for more than two decades (despite there being no published outcome, such as patents). While at the University of Minnesota in 1971 he was shot though not seriously injured (13, 14).

In 1973 Gillard spent a semester in Germany at the Friedrich-Alexander University Erlangen-Nürnberg in the laboratory of Professor Klaus Brodersen (15). Later, in 1981–1982, he spent a sabbatical year travelling and he visited universities in New Zealand (where he was an Erskine Visiting Professor at the University of Canterbury, Christchurch), Australia, the Netherlands (Leiden), and Germany (Freiburg-im-Breisgau), as well as Barbados. He was a Visiting Professor at the Lajos Kossuth University, Debrecen, Hungary in 1983, and acted in an advisory capacity to the University of Brunei from 1985 to 1994. Gillard collaborated extensively with a number of Portuguese colleagues, and as a result during the period 1967 to 2004 he often visited Portugal. Collaboration started with Júlio Domingos Pedrosa da Luz de Jesus, who obtained his first degree from the University of Coimbra, came to Cardiff as a research student (16) in 1974 and was awarded his PhD in 1978 (17). Gillard’s other notably productive collaboration with Portuguese chemists centered on the Instituto Superior Técnico (IST) in Lisbon, involving also the Universidade Nova de Lisboa (S. M. Luz, R. Duarte and J. J. G. Moura). Gillard published nearly 30 papers jointly with João Costa Pessoa (18) of the Centro de Química Estrutural of the IST over the period 1988–2004, almost exclusively dealing with oxovanadium(IV) complexes of amino acids, Schiff bases, and related ligands. Several coworkers were involved, in particular Maria Teresa Duarte, co-author of ten of the papers (19, 20), and Luis Vilas Boas (21). The list of co-authors and their addresses for his final paper (see the end of Section 2, Part II (22)) includes nine Portuguese scientists from five locations (Lisbon, Aveiro, Faro, Savacém and Oeiras), well illustrating his extensive association with chemistry in Portugal.

Gillard had several important collaborations with members of staff in the universities in which he worked. For example at Sheffield there were publications with Professor Ron Mason and the Australians E. Don McKenzie and his good friend Brice Bosnich (‘Bos’) who was then at University College, London, later a Professor at the University of Toronto and afterwards until his retirement at the University of Chicago (23, 24).

At Canterbury Gillard’s Group was of a substantial size and occupied most of the top (fourth) floor of the new Chemistry Department building (Figure 4), so much of his time was spent organising their work and writing up their research results for publication. There were however collaborations with other people in the Department including with the lecturer Brian Heaton (later Professor at the University of Liverpool) on the preparation and characterisation (especially by nuclear magnetic resonance (NMR) techniques) of a variety of rhodium coordination complexes, and with the vibrational spectroscopist Alan Creighton on rhodium complex salts of the acid anion [H(NO3)2], now known to play a role in atmospheric chemistry. At Cardiff there were fruitful collaborations with the Australians Leon Kane-Maguire and Peter Williams. Kane-Maguire had experience of determining the kinetic parameters of relatively slow reactions in solution and with Gillard he did work on reactions of metal complexes that perhaps involved covalently hydrated intermediates. There was extensive collaboration with Williams (over 40 papers), especially on ‘Equilibria in Complexes of N- Heterocyclic Molecules’, and, as mentioned above, he introduced geological inorganic chemistry to Gillard.

Fig. 4

Robert D. Gillard working in his fourth floor office in the University of Kent at Canterbury in 1969 where he was a Reader in Inorganic Chemistry until 1973 (Courtesy of Professor A. W. Addison)

Robert D. Gillard working in his fourth floor office in the University of Kent at Canterbury in 1969 where he was a Reader in Inorganic Chemistry until 1973 (Courtesy of Professor A. W. Addison)

2.7 General Publishing Interests

In addition to the preparation of original research papers and reviews Gillard had a range of other publishing interests. With Professor R. F. Hudson (University of Kent at Canterbury) and Professor J. N. Bradley (University of Essex) Gillard was a cofounding editor of Essays in Chemistry (25) published by Academic Press which appeared regularly from 1970 to 1977, and he was on the founding Editorial Board of the international journal Transitional Metal Chemistry, first published by Chapman and Hall in 1975 and now by Springer. He was on the Editorial Board of the Journal of Coordination Chemistry (26, 27). With his former PhD Supervisor Professor Sir Geoffrey Wilkinson and his friend from Imperial College days Professor Jon A. McCleverty (then at the University of Birmingham, later at the University of Bristol) he edited the seven volumes of Comprehensive Coordination Chemistry published by Pergamon Press in 1987 (2830). In retirement Gillard’s writing activities were diverted to aspects of life in the Edwardian and Victorian eras (see the last paragraph of Section 3, Part II (22)).

3. Research Activities

There is no doubt chemistry was particularly important in Gillard’s life. His love of making chemical discoveries in the laboratory and rapidly rationalising the observations he made was infectious. Clearly whatever caused him to turn to chemistry rather than mathematics at Oxford was a most profound decision for him and later the chemical community as a whole. He published research papers at every university he was at: his Part II work at Oxford, his doctoral work at Imperial college, as a Lecturer at Sheffield University, as a Reader at the University of Kent at Canterbury and as a Professor at Cardiff University.

3.1 University of Oxford: Part II Research Project with Dr H. M. N. H. Irving

At about the time Gillard began his Part II research at Oxford J. C. Bailar in the USA was undertaking research on the optical activity of transition metal complexes that paralleled his studies, illustrating the topical nature of the project set by his supervisor Dr Irving – similar work had very recently been reported from Bailar’s laboratory (31). Gillard’s first publication to appear (but see footnote a to Table I) in the chemical literature was a Letter entitled ‘The 1,2-Propylenediaminetetra-acetato-cobaltate(III) Anion’ that appeared in Nature on 5th November 1960. Gillard was the sole author (see entry A in Table I); when submitted for publication he was working at Burt, Boulton and Haywood Ltd in their Agricultural Department.

Table I

Gillard’s Publications With or Based on Research With Professor Irving

Title Reference Notes
A The 1,2-Propylenediaminetetra-acetato-cobaltate(III) Anion R. D. Gillard, Nature, 1960, 188, 487 a
B Resolution of (±)-Propylenediamine by a Stereospecific Reaction H. Irving and R. D. Gillard, J. Chem. Soc., 1960, 5266–5267 a
C A New Stereospecific Reaction H. Irving and R. D. Gillard, J. Chem. Soc., 1961, 2249
D The Stabilities of the Metal Complexes of Optically Active Amino-acids R. D. Gillard, H. M. Irving, R. Parkins, N. C. Payne and L. D. Pettit, Chem. Commun. (London), 1965, (5), 81–82
E Conformational Aspects of Chelate Rings R. D. Gillard and H. M. Irving, Chem. Rev., 1965, 65, (5), 603–616
F The Isomers of Complexes of α-Amino-acids with Copper(II) R. D. Gillard, H. M. Irving, R. M. Parkins, N. C. Payne and L. D. Pettit, J. Chem. Soc. A, 1966, 1159–1164 b
G Stability Constants of Copper(II) Complexes of Optically Active α-Amino-acids R. D. Gillard, H. M. Irving and L. D. Pettit, J. Chem. Soc. A, 1968, 673–674 c

a It is not altogether clear which of these two articles should be regarded as Gillard’s first publication. In a detailed research CV compiled in 1988 he gives the Note co-authored with Irving as his first publication. This corresponds to the apparent order of completion and submission of the respective manuscripts – the Note to J. Chem. Soc. was received by the Editor on 30th May 1960, while the Letter to Nature appears to have been submitted after Gillard had left Oxford. The particularly rapid refereeing → acceptance → publication sequence characteristic of Letters to Nature in that era may well have resulted in a manuscript posted by Gillard after he had left Oxford overtaking the Note submitted to the Chemical Society – the Letter to Nature was published on 5th November 1960, the Note to J. Chem. Soc. appeared in the last (December) issue of 1960

b The authors’ addresses are given as R. D. G. and N. C. P. at Sheffield, H. M. I., R. M. P. and L. D. P. at Leeds

c The author indicated for correspondence is Pettit. By this time Gillard was at Canterbury

In this short note Gillard pointed out that metal complexes containing only one optically active diamine ligand should have a similar conformation to the diamine (32). This idea originated from his Oxford work with Irving, and subsequently they had several joint publications. The first of these was a note on the optical resolution of propylene diamine by the stereospecific reaction with lævorotatory [CoIII-(+)-pdta] (pdta = propylene-1,2-diamine-tetra-acetate) that appeared in the December 1960 issue of the Journal of the Chemical Society (B in Table I) (33). Again this was based on his Part II research project, and a full paper with Irving entitled ‘A New Stereospecific Reaction’ submitted for publication in November 1960 (Table I, C) continued the theme. This paper (34) highlighted the stereochemistry of the reaction shown in Equation (i) (en = ethane-1,2-diamine).

 (i)

Gillard’s work with Irving on the optical activity of metal complexes was the start of one of his major research themes during his career, and their collaboration continued to when Irving was Professor at Leeds University and Gillard was at the University of Kent at Canterbury. In 1965 when Gillard was at Sheffield they submitted for publication a Chemical Communication (Table I, D) about the stabilities of the metal complexes of optically active amino acids, and a year later, in 1966, a full paper entitled ‘The Isomers of Complexes of α-Amino-acids with Copper(II)’ was published (Table I, F). Before that a short (14 pages) but significant review article that had its origins with background literature work done for his Part II thesis, was published in Chemical Reviews in 1965 (Table I, E). The last of Gillard’s publications with Irving appeared in 1968 when Gillard was at Canterbury. That paper reported further results from their work on copper(II) complexes of optically active α-amino acids and included their formation constants (Table I, G) – Irving was very well known for the determination of formation (stability) constants.

3.2 Imperial College: Research with Professor Geoffrey Wilkinson

Gillard must have had a significant amount of lecturing commitments at Imperial College yet he was able to do much research himself. One of the main areas of chemistry Wilkinson introduced him to was preparative rhodium coordination chemistry which was then topical. A wide range of new rhodium complexes was being prepared and characterised in Wilkinson’s laboratory, with a particular interest in those with hydride ligands that were amenable to study by NMR techniques. The involvement of catalytic amounts of rhodium species in a growing number of homogeneous organic reactions was another important area of intensive research in Wilkinson’s Group. Gillard’s career-long fascination with the chemistry of rhodium is reflected in the number of publications – over 60, from 1963 to 2000 – containing ‘rhodium’ or ‘rhodate’ in their titles. Platinum was another metal of continuing interest, with over 30 publications (1964–2001) featuring its compounds in their titles.

Including later collaborations with Wilkinson, Gillard published 19 papers with him (and one with J. H. Dunlop, Gillard’s first student, without Wilkinson). The first 11 were written and submitted for publication while Gillard was at Imperial College and these and the others are listed in Table II. Six of these papers have only Gillard and Wilkinson as authors, reflecting the tremendous amount of energy Gillard put into his graduate research.

Table II

Gillard’s Rhodium Chemistry Publications with Professor Geoffrey Wilkinson

Title Citation
A Triethylenetetramine Complexes of Cobalt(III) and Rhodium(III) R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1963, 3193–3200
B Hydrido-Complexes of Rhodium(III)- containing Nitrogen Ligands R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1963, 3594–3599
C The Coordination of Ethylenediaminetetraacetate in Complexes of Cobalt(III) and Rhodium(III) R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1963, 4271–4272
D Aquation of the Trisoxalatorhodate(III) Ion R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 870–873
E Complexes of Rhodium(III) with Chloride and Pyridine R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 1224–1228
F Absolute Configurations of Some d 6 Complex Ions of Cobalt, Rhodium, Iridium, and Platinum, and of Complex Ions of Chromium(III) R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 1368–1372
G Adducts of Protonic Acids with Co-ordination Compoundsa R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 1640–1646
H Configurations of Trisdiamine Complexesb J. H. Dunlop, R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 3160–3163
I d-d Transitions in Hydrido-complexes. The Position of the Hydride Ion in the Spectrochemical Series J. A. Osborn, R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 3168–3173
J Activation of Molecular Hydrogen by Complexes of Rhodium-(III) R. D. Gillard, J. A. Osborn, P. B. Stockwell and G. Wilkinson, Proc. Chem. Soc., 1964, 284–285
K Complexes of Ruthenium, Rhodium, Iridium, and Platinum with Tin(II) Chloride J. F. Young, R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 5176–5189
L The Action of Reducing Agents on Pyridine Complexes of Rhodium(III) B. N. Figgis, R. D. Gillard, R. S. Nyholm and G. Wilkinson, J. Chem. Soc., 1964, 5189–5193
M Catalytic Approaches to Complex Compounds of Rhodium(III) R. D. Gillard, J. A. Osborn and G. Wilkinson, J. Chem. Soc., 1965, 1951–1965
N Polarographic Reduction of Complexes of Rhodium(III) R. D. Gillard, J. A. Osborn and G. Wilkinson, J. Chem. Soc., 1965, 4107–4110
O trans- Dichlorotetrakis(pyridine)rhodium(III) salts R. D. Gillard and G. Wilkinson, Inorg. Synth., 1967, 10, 64–67

a Includes hydroxonium salts of trans-[Rh(LL)2X2]+ with LL = en or bipy, X = Cl or Br

b Includes investigation and discussion of circular dichroism and absolute configuration of [Rh(en)3]3+ and [Rh(pn)3]3+

His research at Imperial College was the start of Gillard’s lifelong interest in rhodium chemistry and the relevant publications from this time are listed in Table II. There was a large amount of exciting rhodium chemistry being done that was a part of Wilkinson’s fascination with the rapidly evolving chemistry of some of the less common metals like rhodium as their reactions were explored that often involved then-novel hydride ligands. A huge number of new rhodium compounds were being prepared and characterised which ranged from robust coordination complexes to lower oxidation state organometallic compounds with alkyl moieties with remarkable catalytic properties. Gillard was in the midst of all of this excitement and he was involved in clarifying the oxidation state of hydrido rhodium(III) complexes previously thought to be rhodium(II) species (35), and he extended some of the early studies on catalytic approaches to preparing rhodium(III) complexes via labile lower oxidation state rhodium species (36). To complement this rhodium(II) to rhodium(III) oxidation state reassignment, he later showed that most rhodium complexes earlier believed to contain rhodium(IV) or rhodium(V), such as Claus’s Blue (see several mentions below, also Table S6), were also compounds of rhodium(III) whose oxidising properties resided in such ligands as superoxo rather than in the metal centre.

At Imperial College Gillard also worked with a variety of other metal complexes as well as those of rhodium, and he investigated the nature of so-called ‘platinum blues’ (37) that are a group of polynuclear mixed-valence, metal-metal-bonded, ligand-bridged polymeric complexes, often containing chains of Pt(NH3)2 units with various bridging ligands. In the original platinum blue (Platinblau) of Hofmann (38) acetamide was the bridging ligand, and its intense colour, Gillard and Wilkinson said, was consistent with the presence of mixed oxidation states, while its dichroism, red/blue like [Pt(dmgH)2] (dmgH = dimethylglyoxime), was consistent with a linear chain structure. Later there was a resurgence of interest in platinum blue(s), stemming from observations that incubation of the hydrolysed anticancer drug cisplatin (cis-[Pt(NH3)2Cl2]) with pyrimidines or polynucleotides often resulted in deep blue solutions from which blue solids with high antitumour activity and low renal toxicity were obtained (3941). However, claims for significant anticancer activity were often found to be exaggerated or non-reproducible. Difficulties in characterising these blue materials led to the synthesis of a range of analogues, such as the series of platinum pyrimidine blues prepared from a variety of nucleosides or nucleotides (42). Later Gillard worked on Claus’s Blue, obtained by oxidising rhodium(III) compounds – see Table S6.

Another important area Gillard was involved in at Imperial College was the development of tin(II) chloride as a ligand in platinum, ruthenium, rhodium and iridium complexes that later became important in some catalytic processes (43).

Work within the Wilkinson Group did not exclude research on cobalt(III) complexes that Gillard had gained familiarity with at Oxford. Indeed Gillard’s first publication at Imperial College with Wilkinson was entitled ‘Triethylenetetramine Complexes of Cobalt(III) and Rhodium(III)’ (44) which was soon followed by a paper entitled ‘Hydrogen Bonding in Complexes of Dimethylglyoxime with Cobalt(III)’ (45), and then ‘Absolute Configurations of some d6 Complex Ions of Cobalt, Rhodium, Iridium and Platinum and of Complex Ions of Chromium(III)’ (46) so the chiral properties of cobalt(III) complexes first undertaken at Oxford continued at Imperial College.

Some dimeric copper(II) complexes were prepared and characterised at Imperial College (47), and some years later Gillard returned to copper(II) complexes after leaving Imperial College (see Table S3). Later papers on dimeric complexes involved Co(III) (1969) or VO2+ (1973) rather than Cu(II). He maintained an interest in copper for many years, the last paper devoted to this metal appearing in 1995 (48). Here, and in several publications from the period 1977 to 1980 (by which time Gillard was well established in Cardiff), the ligands were various amino acids.

Gillard did a huge amount of research across a wide range of inorganic transitional metal chemistry at Imperial College, and it is clear his serendipitous move to do research with Professor Wilkinson was a major event that stimulated and shaped much of his later professional research career.

3.3 University of Sheffield: Independent Research

During his time at Imperial College much of Gillard’s research followed directions set by Professor Wilkinson and topics pursued within his group, but Gillard also had considerable independence that of course increased immensely when he moved to the University of Sheffield in 1964. Here he was able to concentrate more on his personal research interests and establish his own research agenda while continuing to publish with both Irving and Wilkinson. He turned enthusiastically to an area of coordination chemistry he worked on at Oxford: the optical activity properties of metal complexes and soon he expanded on what he had done previously. There were several joint papers with Professor Irving (see Section 3.1 and Table I), and his independent work included the first papers in series (49, 50) such as ‘Adducts of Coordination Compounds’ (Table S1) and ‘Optically-active Coordination Compounds’ (Table S2). The former ran to 15 parts and continued until 1990; while the latter, his most extensive series of papers, comprised 51 parts, of which the first 37 appeared at frequent intervals between 1965 and 1975, the next 13 roughly annually until 1989, and the final part in 1995–1996. There was also a short review entitled ‘Optically-Active Coordination Compounds’ published in 1967 (5153) that followed the publication of his more substantial review ‘The Cotton Effect in Coordination Compounds’ (54). Some papers published or submitted for publication while Gillard was at Sheffield University are listed in Tables S1 and S2.

Several of the papers in the ‘Adducts of Coordination Compounds’ series (Table S1) relate to the once-elusive hydrogen dinitrate anion [H(ONO2)2]. Schultz may have made a few species containing this anion in his investigation, briefly reported (55) in 1869, of solubilities of nitrates in nitric acid. Ditte prepared several acid nitrates M(NO3xHNO3 (M = K, Rb, Tl, NH4) in the course of an extensive study of reactions of a range of nitrates with fuming nitric acid; Ditte’s results, published (5660) in 1879, were largely confirmed by Wells and Metzger (1901) (61) and by Chédin, Leclerc and Fénéant (1947) (62, 63). Chédin and Fénéant subsequently reported that their Raman study of KNO3 in HNO3 indicated the presence of a species [(HNO3)2NO3] at 268 K (64). Hedin (65) prepared the first nitric acid adduct of a transition metal complex [Pt(py)4Cl2](NO3)2·2HNO3·2H2O and Poulenc later in the course of his study of reactions of [RhBr6]3– with pyridine (66), isolated shiny yellow triangular prisms which analysed as [Rh(py)4Br2]NO3·HNO3. However, it was not until the mid-1960s that his product was re-formulated, mainly on the basis of infrared spectroscopy and conductivity measurements, as a hydrogen dinitrate salt, trans-[Rh(py)4Br2][O2NO·H·ONO2] (67, 68). At the time of his reformulation of Poulenc’s salt Gillard also showed that the vibrational spectrum of [Ph4As]NO3·HNO3 was consistent with its containing symmetrically H-bonded [H(NO3)2] (69). In 1967 single crystal X-ray studies of trans-[Rh(py)4Br2]NO3·HNO3(70) and of [Ph4As]NO3·HNO3 (71) confirmed the presence of the [H(ONO2)2] anion in both salts, albeit in different configurations (7275). The last two members of Gillard’s ‘Adducts of Coordination Compounds’ series report the isolation and characterisation of several more hydrogen dinitrate salts of complexes of pgms, for example of trans-[Ru(py)4Cl2]+ (76) and of trans-[IrL4X2)]+ (L = pyridine, perdeuteriopyridine or 4-methylpyridine; X = Cl or Br) (7779). Since Gillard’s investigation of hydrogen dinitrates there has been sporadic interest in compounds containing this anion. For example, an iron-substituted polyoxometalate/hydrogen dinitrate system – specifically [FeIIIW11O39·H(ONO2)2]5– – was in 2006 reported to be a highly reactive catalyst for aerobic oxidation of thioethers (80). In recent years the hydrogen dinitrate anion, as one of a number of species in nitrate clusters with nitric acid and water (81) has become of considerable interest in relation to chemistry of the atmosphere.

The first paper in the ‘Optically Active Co-ordination Compounds’ series (Table S2) was on the optical configurations of bisethylenediamine complexes of cobalt(III) with his PhD student Keith Garbett who must have worked quickly to have produced such a volume of results in such a short period of time (82). The very small number of papers from this series detailed in Table S2 illustrate the range of complexes and topics covered in these 51 papers, published over a period of some 30 years. Thus the nine citations in Table S2 include such favourite subjects as rhodium complexes, copper complexes (especially with amino acids), circular dichroism and reaction mechanisms.

Work on what became the series ‘Isomers of α-Aminoacids with Copper(II)’ (Table S3) and ‘Reactions of Complex Compounds of Cobalt’ (Table S4) was probably initiated while Gillard was at Sheffield, and the paper entitled ‘Stability Constants of Copper(II) Complexes of Optically Active α-Amino-acids’ (83) forms a link back to his research at Oxford.

3.4 University of Kent at Canterbury: Continued Independent Research

Gillard’s move in 1966 to the almost completed Chemistry Department at the University of Kent at Canterbury (84) with new laboratories, new equipment and good funding coupled with a growing number of youthful enthusiastic researchers from a variety of universities gave him a marvellous opportunity to work productively with vigour, to expand his research group, and to enhance his already considerable personal reputation. His main research areas at Canterbury included cobalt and some copper chemistry, much rhodium chemistry as well as bioinorganic chemistry which was facilitated by the Medical Research Council funding his Research Group on Biological Inorganic Chemistry.

Early in his time at Canterbury Gillard began his series of papers entitled ‘Reactions of Complex Compounds of Cobalt’ that are summarised in Table S4. Most of the work for the opening paper, presumably done at Sheffield, gave a novel explanation for the then-much-discussed apparently ambiguous second-order rate law for base hydrolysis of cobalt(III)-ammine complexes (85). The simplest interpretation of the established rate law was rate-determining attack by hydroxide at the metal centre (86). However, both in the light of the difficulty of access of the hydroxide to the low-spin t2g6 Co(III) centre and in the absence of any other well-established bimolecular substitutions at this ion, an alternative SN1CB mechanism had also been proposed, in which rapid reversible loss of an ammine or amine proton was followed by rate-limiting dissociation of the conjugate base (8789). Gillard’s suggestion that the rate-determining step in such base hydrolyses was electron transfer from a hydroxyl ion to cobalt(III), to give a labile cobalt(II) complex intermediate, offered a neat way of circumventing the vexing SN2 versus SN1CB question. This idea is consistent both with many observations from preparative cobalt chemistry, and with differences in kinetic behaviour for base hydrolyses of between cobalt(III), rhodium(III) and chromium(III) complexes (85). However, there is rather little supporting evidence from similar systems. [Co(NH3)5(NO2)]2+ is not aquated directly in an acetate buffer, but it does react to give cobalt in the +2 oxidation state (9092). This presumably results from initial electron transfer to the cobalt; the electron probably comes from the anion rather than from the cationic ligands, as in base hydrolysis, or thermal decomposition of [Co(NH3)6]3+ and [Co(NH3)5X]2+ salts (93). Indeed hydroxide can be reducing when coupled to strongly oxidising systems, as in the mechanism suggested for base hydrolysis of [M(diimine)3]n + {M = Fe, Ru, Os; diimine = phen or bipy; n = 3} (94) (cf. the covalent hydration discussion in Section 2.1.1, Part II (22)). As with so many of his novel suggestions, this proposal attracted criticism, with Endicott stating that “the Gillard mechanism can be ruled out on both kinetic and energetic grounds” – and indeed was “outrageous” (95).

By Part 4 (96) of the series ‘Reactions of Complex Compounds of Cobalt’ (Table S4) Gillard’s penchant for looking into long-published (but also long-ignored!) oddities had led him to investigate the green products, described in the 1920s, which had been obtained (97, 98) on reacting cobalt(III) salicylatotetrammine or salicylatobisethylenediamine complexes with nitric acid. He suggested, largely on the basis of electronic spectra and circular dichroism data, that the colour was due to ligand-oxidation and that the green complexes were cobalt(III) species containing 5-nitrososalicylate rather than the cobalt(IV)-5-nitrosalicylate analogues proposed by the original authors (99).

A more recent example of his interest in all-but-forgotten puzzles involved the so-called ‘Tipper’s Compound’. In 1955 C. F. H. Tipper described the reaction between H2PtCl6 and cyclopropane, suggesting the formula (PtCl2·C3H6)2 for his product (100, 101). A few years later a polynuclear structure was proposed on the basis of infrared and NMR spectra (102); then in 1969 Gillard, on the basis of mass spectrometry and additional infrared evidence, argued that the compound was tetrameric dichlorotrimethylene-platinum(IV) (103).

Even before going to Canterbury Gillard was interested in the potential pharmaceutical applications of inorganic complexes. This interest was fostered by the founding of the Medical Research Council Research Group on Biological Inorganic Chemistry at Canterbury; MRC funding began very soon after he went to Canterbury. Practical work in biological areas was facilitated by Gillard recruiting a number of microbiologists such as Richard Dainty (104) and Colin Thorpe (105), together with several others who had some experience of metal-biological interactions such as Stuart Laurie (106). The result was an enthusiastic group of ‘bioinorganic’ researchers.

Gillard’s interest in this area was probably prompted by reports of the antibacterial, antitumour and wound healing properties and topical infection control of stable metal complexes of the type [M(diimine)3]n + {M = for example Fe, Ru; diimine = phen or bipy}. Effects of this type of metal-diimine complex on cells and organisms seem to have been first reported, specifically for [Fe(bipy)3]2+, in the late 1930s by Emilio Beccari (107111). In the 1950s a wider-ranging study was described by a group of Australian chemists led by F. P. Dwyer (112117). This work was later developed by several groups, including that of his younger colleague Shulman (118120). Gillard was intrigued by the dramatic elongation of growing cells brought about by low levels (a few ppm) of platinum(IV) complexes. These abnormal filamentous cells could be several hundred times longer than normal cells (121, 122).

Gillard started publishing his 12-part series ‘Coordination Compounds and Micro-Organisms’ (Table S5) in 1969 (123); the last part appeared in 1989 (124). His work on this series was carried out over more than two decades, during which time Gillard maintained a strong interest in the area. During this time he will have noted such relevant publications as the reported bacteriostatic effects of [Ru(phen)3)]2+ and related complexes (125) and by the description of the cholinolytic activity of 3,4,7,8-tetramethyl-1,10-phenanthroline complexes of copper(II) and nickel(II) (126). He may well also have been influenced by the later research of Margaret Farago and her group at Imperial College on the effects of added inorganic species on the growth of various aquatic plants (see below).

An early product of the practical work, reported in Part 1, was the investigation of the bacteriostatic activity of complexes of a range of Co(III), Rh(III), and Ir(III) complexes containing substituted pyridines, 2,2′-bipyridine, 1,10-phenanthroline, or ethane-1,2-diamine (127). Part 10 of this series derives from the 1981 conference at Bristol on the chemistry of the platinum metals – the first such on an international scale. This was the first of a series of eight triennial conferences on this area, one example of the long-standing collaboration between Johnson Matthey and the Royal Society of Chemistry (and its predecessor, the Chemical Society) (128). Gillard’s contribution described some effects of rhodium complexes on bacterial growth (129). The final part in the series dealt with the antibacterial activity of rhodium complexes of S- nicotine (124). Interestingly, he returned to these rhodium-nicotine complexes a decade later (130132). This was in a paper entitled ‘Stereoselectivity in Rhodium Antibiotics’, which reported on the concentration-dependence of the bactericidal properties of the enantiomeric rhodium(III)-nicotine complexes trans-[Rh(S-(–))-nicH+)4Cl2](PF6)5, trans-[Rh(R-(+)-nicH+)4Cl2](PF6)5 and trans-[Rh(RS-(+)-nicH+)4Cl2](PF6)5. This work was claimed to be the first to demonstrate stereoselective prevention of bacterial growth by one enantiomer of a metal complex. Gillard had earlier briefly reviewed the antibacterial properties and redox behaviour of rhodium complexes with pyridine and substituted pyridines (133). Whereas several rhodium complexes have considerable bactericidal properties there are very few reports of significant antitumour capability. Indeed a recent review (134) (101 references) of the role of pgms in cancer therapy mentions just one rhodium compound – a rhodium(I) complex [RhCl(COD)(NHC)], 1, where COD is cycloocta-1,5-diene and NHC is an N-heterocyclic carbene ligand derived from caffeine. This compound shows multiple anticancer properties and antibacterial activity (135). Other earlier publications by Gillard in this area but not included in the ‘Coordination Compounds and Micro-Organisms’ series include a significant review on metal-protein interactions (136) with Stuart Laurie.

Shortly after starting the series of papers on microorganisms Gillard began publishing another rhodium-centred series of papers ‘Oxidants Containing Rhodium’ (Table S6) and at the same time a series of papers on metal complexes, mainly of nickel, as probes for the structure of solvents (Table S7). The former consists of a disparate collection of papers, reviews and a conference abstract, apparently gathered together during the preparation of the manuscript for what was to be labelled as Part 8. Most papers in Table S6 (and a paper entitled ‘Oxidants Containing Rhodium’ but not included in the series!) deal with superoxo complexes. Their main conclusion (137) is that nearly all the substances generated in water and said to involve rhodium-(IV), -(V) and -(VI) species (138, 139) are in fact superoxide complexes of rhodium(III) (140144). Eventually, after his move to Cardiff, Gillard published the last paper in the series in which was reported X-ray photoelectron spectroscopy on so-called Claus’s Blue (145147). This is one of several long-known blue or violet rhodium species obtained by chlorine, peroxoanion (148, 149), or electrolytic (66, 150) oxidation of rhodium(III). This enabled the assignment of the oxidation state of 3+ to the rhodium in this species, indicating that it too was a superoxo-Rh complex. The formula proposed (151) for Claus’s Blue was Ba[(H2O)4RhIII(μ-O2)(μ-OH)RhIII(OH2)4], rather than the [RhVIO4]2– originally suggested by Claus.

The series of papers devoted to the use of metal complexes to probe solvent structure (Table S7) reflects Gillard’s abiding interest in the development of coordination chemistry. The nickel salt he selected for all but the last member of the series was bis-meso-(stilbenediamine) nickel(II) acetate, Ni(stien)2(OAc)2 (stien = stilbenediamine = H2NC6H4CH:CHC6H4NH2). This salt is one of the so-called Lifschitz salts – prepared and investigated in the mid-20th century by such worthies as Mann (152, 153), Lifschitz (154156) and Pfeiffer (157), and later by several other groups (158161). Lifschitz salts may be obtained in yellow or orange diamagnetic form or in blue or violet paramagnetic form, in some cases in both forms, depending on the coordination number and stereochemistry at the Ni2+ centre (coordination number 4 planar versus coordination number 6 octahedral respectively), which in turn depends on the natures of the diamine (generally an N,N-dialkylethane-1,2-diamine or stilbenediamine), of the anion, and of the solvent (coordinating or non-coordinating) used for their preparation. Equilibrium between the two forms may be observed in solution in systems where the coordinating powers of the anion and solvent are appropriately balanced. Gillard used the consequent marked changes in colour with change of stereochemistry to monitor changes in solvent structure on adding various cosolvents – alcohols, ketones, amides, or glycol ethers – to their aqueous solutions (162165). Appropriate plots of ratios of yellow to blue forms as a function of solvent composition reflected changes in structure of the mixed solvents analogous to those established by various techniques for alcohol-water and similar binary solvent systems (166). This approach represents a major advance from earlier similar work on solvent structure (167). This had been based on very small changes in visible absorption spectra of square-planar [Co(meab)], 2. Nevertheless the results, particularly in aqueous pyridine, were deemed to be “intriguing” (168170). Gillard and Sutton’s nickel probes proved better than [Co(meab)] in that their stereochemical change resulted in much bigger changes in spectra. Interestingly, Gillard switched to cobalt(III) and the rather different probe of interactions between [Co(en)3]3+ and anions for the final paper in this series – published almost 20 years later, long after he had left Canterbury. Here, differences in the concentration-dependence of the circular dichroism spectra of sulfate and perchlorate ion-pairs are ascribed to a balance between ion-pairing and selective solvation (171). Then, 14 years on (in 2003), a paper on the salting-in of uncharged cobalt(III), chromium(III), and copper(II) complexes of natural amino acids by salts such as MgCl2 or AgNO3 effectively provided a postscript to the series. The existence of significant complex-salt interactions was illustrated by the isolation of adducts such as trans- [Cu(gly)2]·2AgNO3 (172).

The seven years or so Gillard spent at Canterbury proved to be an exceptionally productive period in terms of the diversity of research undertaken – from fundamental work on classical inorganic complexes (173176) through biochemical to medically-related topics – and the number of papers published (slightly more than one hundred). The MRC funding of key aspects of his work very much helped facilitate Gillard’s industriousness that continued when he was a Professor at Cardiff, though he had considerably fewer coworkers there.

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References and Notes

  1. 1.
    Harry Munroe Napier Hetherington Irving’s wide-ranging research interests included structural and solution chemistry of coordination complexes. He moved from Oxford (where he was in Gillard’s time Vice President of St Edmund Hall as well as University Demonstrator in Chemistry) to the chair of Inorganic and Structural Chemistry at the University of Leeds in 1961. He retired in 1971, but in 1976 travelled to the University of Cape Town (UCT), initially for a three month stay. In practice he stayed on in South Africa until his death in 1993. He inaugurated the chair of Analytical Science at UCT in 1979, remaining in that post until his second retirement, at the age of 80, in 1985 (2, 3). Gillard invoked the Irving-Williams Series (4) from time to time and shared Williams’s interest in matters inorganic, biochemical and medical; R. J. P. Williams was one of the examiners for Gillard’s BSc thesis
  2. 2.
    A. T. Hutton, Trans. Roy. Soc. S. Africa, 1994, 49, (2), 256–258 LINK https://doi.org/10.1080/00359199409520314
  3. 3.
    R. J. P. Williams and R. D. Gillard, Polyhedron, 1987, 6, (1), 1 LINK https://doi.org/10.1016/S0277-5387(00)81231-0
  4. 4.
    H. Irving and R. J. P. Williams, J. Chem. Soc., 1953, 3192–3210 LINK https://doi.org/10.1039/JR9530003192
  5. 5.
    Nobel Prize Winner, jointly with E. O. Fischer, in 1973 (6); knighted in 1976
  6. 6.
    ‘The Nobel Prize in Chemistry 1973: Ernst Otto Fischer and Geoffrey Wilkinson’, “Nobel Prizes and Laureates”, The Nobel Foundation, Stockholm, Sweden, 1973 LINK https://www.nobelprize.org/prizes/chemistry/1973/summary/
  7. 7.
    Anthony J. Poë (later Professor of Chemistry at the University of Toronto) was at Imperial College and registered for a PhD (completed in 1961). Gillard had a position at Imperial College as a vacancy became available thanks to Poë being invited by Professor Fred Basolo to supervise the work of his research group at North Western University at Evanston, Illinois while Basolo spent a sabbatical in Rome during the year 1961–1962 (8)
  8. 8.
    F. Basolo, ‘Foreign Guests Hosted: A. J. Poë’, in “From Coello to Inorganic Chemistry: A Lifetime of Reactions”, Profiles in Inorganic Chemistry, Ch. 6, Springer Science and Business Media, New York, USA, 2002, p. 207 LINK https://doi.org/10.1007/978-1-4615-0635-5_6
  9. 9.
    This is dated July 1964; it has ix+103 pages. There are 95 references, the earliest dating from 1885, several are pre-1914. This spread of dates and the occasional esoteric source, are an early example of Gillard’s wide-ranging scanning of the chemical literature (10)
  10. 10.
    R. D. Gillard, “Spectroscopic Studies on Complex Compounds of Transition Metal Compounds”, PhD Thesis, Department of Chemistry, Imperial College, London, UK, July, 1964, 112 pp LINK https://spiral.imperial.ac.uk/bitstream/10044/1/16476/2/Gillard-RD-1964-PhD-Thesis.pdf
  11. 11.
    Dunlop subsequently moved to the Technische Hochschule, München, Germany. Payne later became a Professor at the University of Western Ontario in Canada. Garbett later worked at Northwestern University with Professor I. M. Klotz, using Mössbauer spectra to study hemerythrin, before going on to work on corrosion in nuclear power plants at the UK’s Central Electricity Generating Board (CEGB)
  12. 12.
    M. E. Clissold, P. Leverett, P. A. Williams, D. E. Hibbs and E. H. Nickel, Canadian Mineral., 2007, 45, (2), 317–320 LINK https://doi.org/10.2113/gscanmin.45.2.317
  13. 13.
    The University’s official information publication reported, in issue 32 of May 25, that “Robert D. Gillard, chemistry, visiting professor from England, was shot Saturday in his office. He was taken to U Hospitals, where he is listed in satisfactory condition. Suspect was taken into custody pending investigation” (14)
  14. 14.
    University of Minnesota Brief, 1971, 1, (32), 2 LINK http://hdl.handle.net/11299/98647
  15. 15.
    A decade later, collaboration with Brodersen was reflected in a visit to Cardiff by Brodersen’s protégé Hans Ulrich Hummel (see the paragraph on gravimetric analysis of [Fe(phen)2(CN)2] hydrate toward the end of Section 2.1.1, Part II (22) and the endnote cited there)
  16. 16.
    At Cardiff Gillard supervised several graduates of Portuguese universities for MSc or PhD degrees, an early example being Jaime Alejandro Arce Sagüés, whose MSc, completed in 1977, dealt with several ruthenium(III)-diimine complexes
  17. 17.
    On his return to Portugal he was appointed to the Chemistry Department of the University of Aveiro, becoming a Professor in 1979 and acting as Minister of Education 2001–2002. He published a dozen papers with Gillard over the years 1977 to 1990. These mainly deal with complexes of rhodium(III) and molybdenum(VI); he contributed to three papers in the “Optically-Active Compounds” series
  18. 18.
    Gillard’s postgraduate student Ray Wootton worked both with Costa Pessoa and with Frausto da Silva in Portugal
  19. 19.
    Her contributions can be traced through the latest Part, viz. “Preparation and characterisation of new oxovanadium(IV) Schiff Base complexes derived from amino acids and aromatic o-hydroxyaldehydes” (20)
  20. 20.
    J. Costa Pessoa, I. Cavaco, I. Correia, M. T. Duarte, R. D. Gillard, R. T. Henriques, F. J. Higes, C. Madeira and I. Tomaz, Inorg. Chim. Acta, 1999, 293, (1), 1–11 LINK https://doi.org/10.1016/S0020-1693(99)00196-6
  21. 21.
    L. F. Vilas Boas worked in Gillard’s group in Cardiff and later was a colleague of Costa Pessoa in Lisbon. Gillard published nine papers (1977–1992) and at least three conference abstracts with Vilas Boas
  22. 22.
    J. Burgess and M. V. Twigg, Johnson Matthey Technol. Rev., 2021, 65, (1), 23–43 LINK https://www.technology.matthey.com/article/65/1/23-43/
  23. 23.
    The Australian Professor Brice Bosnich was elected a Fellow of The Royal Society in 2000 and after retirement at the age of 70 he left Chicago and returned to Australia where he questioned the validity of some global warming claims. He died in 2015 (24)
  24. 24.
    J. D. Crowley, W. G. Jackson and S. B. Wild, Aust. J. Chem., 2016, 69, (5), 485–488
  25. 25.
    The seven volumes published consisted of short reviews aimed at undergraduates and postgraduates
  26. 26.
    J. D. Atwood, Department of Chemistry, University of Buffalo, New York, USA, February, 2017, personal correspondence
  27. 27.
    J. Coord. Chem., 1997, 41, (3), a LINK https://doi.org/10.1080/00958979708023568
  28. 28.
    Gillard’s strong Portuguese connections are reflected in the inclusion of two substantial chapters by three of his collaborators from that country (29, 30)
  29. 29.
    L. F. Vilas Boas and J. Costa Pessoa, ‘Vanadium’, in “Comprehensive Coordination Chemistry”, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Vol. 3, ch. 33, Pergamon Press, Oxford, UK, 1987, pp. 453–583
  30. 30.
    J. D. Pedrosa de Jesus, ‘Hydroxy Acids’, in “Comprehensive Coordination Chemistry”, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Vol. 2, ch. 15.7, Pergamon Press, Oxford, 1987, pp. 461–486
  31. 31.
    E. J. Corey and J. C. Bailar, J. Am. Chem. Soc., 1959, 81, (11), 2620–2629 LINK https://doi.org/10.1021/ja01520a006
  32. 32.
    R. D. Gillard, Nature, 1960, 188, (4749), 487 LINK https://doi.org/10.1038/188487a0
  33. 33.
    H. Irving and R. D. Gillard, J. Chem. Soc., 1960, 5266–5267
  34. 34.
    H. Irving and R. D. Gillard, J. Chem. Soc., 1961, 2249
  35. 35.
    B. N. Figgis, R. D. Gillard, R. S. Nyholm and G. Wilkinson, J. Chem. Soc., 1964, 5189–5193 LINK https://doi.org/10.1039/JR9640005189
  36. 36.
    R. D. Gillard, J. A. Osborn and G. Wilkinson, J. Chem. Soc., 1965, 1951–1965 LINK https://doi.org/10.1039/JR9650001951
  37. 37.
    R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 2835–2837
  38. 38.
    K. A. Hofmann and G. Bugge, Ber. Dtsch. Chem. Ges., 1908, 41, (1), 312–314 LINK https://doi.org/10.1002/cber.19080410159
  39. 39.
    P. J. Davidson, P. J. Faber, R. G. Fischer, S. Mansy, H. J. Peresie, B. Rosenberg and L. VanCamp, Cancer Chemother. Rep., 1975, 59, (2), 287–300
  40. 40.
    B. Rosenberg, Cancer Chemother. Rep., 1975, 59, (3), 589–598
  41. 41.
    R. J. Speer, H. Ridgeway, L. M. Hall, D. P. Stewart, K. E. Howe, D. Z. Lieberman, A. D. Newman and J. M. Hill, Cancer Chemother. Rep., 1975, 59, (3), 629–641
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    T. V. O’Halloran, P. K. Mascharak, I. D. Williams, M. M. Roberts and S. J. Lippard, Inorg. Chem., 1987, 26, (8), 1261–1270 LINK https://doi.org/10.1021/ic00255a016
  43. 43.
    J. F. Young, R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 5176–5189 LINK https://doi.org/10.1039/JR9640005176
  44. 44.
    R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1963, 3193–3200 LINK https://doi.org/10.1039/JR9630003193
  45. 45.
    R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1963, 6041–6044
  46. 46.
    R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1964, 1368–1372 LINK https://doi.org/10.1039/JR9640001368
  47. 47.
    R. D. Gillard, D. M. Harris and G. Wilkinson, J. Chem. Soc., 1964, 2838–2840
  48. 48.
    H. O. Davies, R. D. Gillard, M. B. Hursthouse and A. Karaulov, J. Chem. Soc . Dalton Trans., 1995, (14), 2333–2336 LINK https://doi.org/10.1039/DT9950002333
  49. 49.
    The vagaries of research and publication occasionally led to irregularities in numbering Parts of series. Thus, for instance, there are (a very few) papers included in two series (see, e.g., the footnotes to Table S5) and several Parts of the series “Equilibria in Complexes of N- Heterocyclic Molecules” are missing –though this series has two Part 50s. Moreover there are several publications which were not assigned to appropriate series despite their being central to the subjects of the respective series, for example “Direct Evidence for Existence of a Covalently Hydrated Coordination Compound” (50)
  50. 50.
    R. D. Gillard, L. A. P. Kane-Maguire and P. A. Williams, Transition Met. Chem., 1976, 1, 247
  51. 51.
    A preliminary heavily abbreviated version of Gillard’s Meldola Lecture (52), followed by a short article on Raphael Meldola himself, appeared earlier that year (53)
  52. 52.
    R. D. Gillard, Chem. Brit., 1967, 3, (5), 205–211
  53. 53.
    R. D. Gillard, Chem. Brit., 1967, 3, (1), 1–2
  54. 54.
    R. D. Gillard, ‘The Cotton Effect in Coordination Compounds’, in “Progress in Inorganic Chemistry”, ed. F. A. Cotton, Vol. 7, John Wiley and Sons Inc, New York, USA, 1966, pp. 215–276 LINK https://doi.org/10.1002/9780470166086.ch4
  55. 55.
    C. Schultz, Z. Chem., 1869, 5, 531–532
  56. 56.
    This paper (57) was summarised (58, 59) and the results included in (60). See page 293 of (60), “Deuxième Partie: Sels Ternaires Oxygénés”, where it is specifically stated that the nitrates of rubidium and of caesium, like those of potassium and of ammonium, dissolve in fuming nitric acid to give “acid nitrates”
  57. 57.
    A. Ditte, Ann. Chim. Phys., Series 5, 1879, 18, 320–345 LINK https://gallica.bnf.fr/ark:/12148/bpt6k348582/f319.image
  58. 58.
    A. Ditte, Comptes Rendus, 1879, 89, 576–579 LINK https://gallica.bnf.fr/ark:/12148/bpt6k3046j/f612.item.r=a
  59. 59.
    A. Ditte, Comptes Rendus, 1879, 89, 641–643 LINK https://gallica.bnf.fr/ark:/12148/bpt6k3046j/f685.image.r=a
  60. 60.
    A. Ditte, “Étude Générale des Sels: Deuxieme Partie: Sels Ternaires Oxygénés”, Leçons Professées à la Faculté des Sciences de Paris, H. Dunod et E. Pinat, Paris, France, 1906, 382 pp, p. 293 LINK https://gallica.bnf.fr/ark:/12148/bpt6k90616v.texteImage
  61. 61.
    H. L. Wells and F. J. Metzger, Am. Chem. J., 1901, 26, 271–275
  62. 62.
    J. Chédin and S. Fénéant, Comptes Rendus, 1947, 224, 930–932 LINK https://gallica.bnf.fr/ark:/12148/bpt6k3176m/f934.image
  63. 63.
    J. Chédin, R. Leclerc and R. Vandoni, Comptes Rendus, 1947, 225, 734–736 LINK https://gallica.bnf.fr/ark:/12148/bpt6k3177x/f734.image
  64. 64.
    J. Chédin and S. Fénéant, Comptes Rendus, 1949, 228, 242–244 LINK https://gallica.bnf.fr/ark:/12148/bpt6k31801/f242.item
  65. 65.
    S. G. Hedin, Acta Univ. Lund, Sect. 2, 1886, 22, 1–6
  66. 66.
    P. Poulenc, Ann. Chim., 1935, 11, (4), 567–657
  67. 67.
    Gillard suggested this reformulation at the Autumn Meeting of the Royal Society of Chemistry at Nottingham in September 1965 (Abstract B4), then published it the following year (68). This paper also reports the preparation of a number of similar compounds, trans-[MA4X2](O2NO·H·ONO2),with M = Co or Rh, A = pyridine or ½(bipyridine) and X = CI or Br
  68. 68.
    R. D. Gillard and R. Ugo, J. Chem. Soc . A, 1966, 549–552 LINK https://doi.org/10.1039/J19660000549
  69. 69.
    B. D. Faithful, R. D. Gillard, D. G. Tuck and R. Ugo, J. Chem. Soc . A, 1966, 1185–1188 LINK https://doi.org/10.1039/J19660001185
  70. 70.
    G. C. Dobinson, R. Mason and D. R. Russell, Chem. Commun. (London), 1967, (2), 62–63 LINK https://doi.org/10.1039/C19670000062
  71. 71.
    B. D. Faithful and S. C. Wallwork, Chem. Commun. (London), 1967, (23), 1211 LINK https://doi.org/10.1039/C19670001211
  72. 72.
    Disappointingly, infrared-Raman spectroscopic, X-ray diffraction (73) and neutron-scattering (74) studies of Cs[H(ONO2)2] failed to establish the position of the proton. However, a subsequent neutron diffraction study of trans-[Rh(py)4Cl2]NO3·HNO3 highlighted the disorder that probably explains the difficulty in locating the exact location of the H atom in the hydrogen dinitrate anion (75)
  73. 73.
    J. M. Williams, N. Dowling, R. Gunde, D. Hadži and B. Orel, J. Am. Chem. Soc., 1976, 98, (6), 1581–1582 LINK https://doi.org/10.1021/ja00422a051
  74. 74.
    J. Rozière and C. V. Berney, J. Am. Chem. Soc., 1976, 98, (6), 1582–1583 LINK https://doi.org/10.1021/ja00422a052
  75. 75.
    J. Rozière, M. S. Lehmann and J. Potier, Acta Crystallogr., Sect. B: Struct. Sci., 1979, B35, (5), 1099–1102 LINK https://doi.org/10.1107/S0567740879005653
  76. 76.
    N. S. Al-Zamil, E. H. M. Evans, R. D. Gillard, D. W. James, T. E. Jenkins, R. J. Lancashire and P. A. Williams, Polyhedron, 1982, 1, (6), 525–534 LINK https://doi.org/10.1016/S0277-5387(00)81606-X
  77. 77.
    (78); many years earlier trans-[Ir(py)4Cl2)][H(ONO2)2]had been mentioned as an aside in a short paper on synthesis of iridium(III) complexes (79)
  78. 78.
    R. D. Gillard and S. H. Mitchell, Polyhedron, 1987, 6, (10), 1885–1899 LINK https://doi.org/10.1016/S0277-5387(00)81100-6
  79. 79.
    R. D. Gillard and B. T. Heaton, Chem. Commun. (London), 1968, (2), 75 LINK https://doi.org/10.1039/C1968000075A
  80. 80.
    N. M. Okun, J. C. Tarr, D. A. Hilleshiem, L. Zhang, K. I. Hardcastle, C. L. Hill, J. Mol. Catal. A: Chem., 2006, 246, (1–2), 11–17 LINK https://doi.org/10.1016/j.molcata.2005.10.006
  81. 81.
    N. Heine, T. I. Yacovitch, F. Schubert, C. Brieger, D. M. Neumark and K. R. Asmis, J. Phys. Chem. A, 2014, 118, (35), 7613–7622 LINK https://doi.org/10.1021/jp412222q
  82. 82.
    K. Garbett and R. D. Gillard, J. Chem. Soc., 1965, 6084–6100 LINK https://doi.org/10.1039/JR9650006084
  83. 83.
    R. D. Gillard, H. M. Irving and L. D. Pettit, J. Chem. Soc. A, 1968, 673–674 LINK https://doi.org/10.1039/J19680000673
  84. 84.
    At the University of Kent at Canterbury chemists were first housed in a temporary ‘hut’ near Eliot College and they moved into the new Chemistry Building well before it was formerly opened by the Chancellor Her Royal Highness Princess Marina Duchess of Kent on 20th October 1967 when most of the offices and laboratories were, or in the process of being, occupied. The chemistry building had four floors for Radiochemistry (Professor G. Martin, later Dean of Natural Sciences and Deputy Vice-Chancellor), Physical Chemistry (Professor E. F. Caldin), Organic Chemistry (Professor R. F. Hudson) and the top floor Inorganic Chemistry (Dr R. D. Gillard). Spacious teaching laboratories were in a single story annex. Today the building is known as the Ingram Building
  85. 85.
    R. D. Gillard, J. Chem. Soc. A, 1967, 917–922 LINK https://doi.org/10.1039/J19670000917
  86. 86.
    F. Basolo and R. G. Pearson, “Mechanisms of Inorganic Reactions: A Study of Metal Complexes and Solutions”, 2nd Edn., John Wiley and Sons, New York, USA, 1967, p. 177
  87. 87.
    Comparison of H/D exchange rates with those for base hydrolysis lends strong support to the SN1 CB mechanism for the latter. See for example (88, 89)
  88. 88.
    C. K. Poon and M. L. Tobe, Chem. Commun. (London), 1968, (3), 156–158 LINK https://doi.org/10.1039/C19680000156
  89. 89.
    M. L. Tobe and J. Burgess, “Inorganic Reaction Mechanisms”, Addison-Wesley Longman, Harlow, UK, 1999, p. 158
  90. 90.
    D. Banerjea, J. Inorg. Nuclear Chem., 1967, 29, (11), 2795–2805 LINK https://doi.org/10.1016/0022-1902(67)80019-8
  91. 91.
    Redox catalysis of substitution at analogous chromium(III) complexes is well-known, as for example in the facile preparation of tris(diamine)chromium(III) salts (see for example (92)). Gillard also used zinc reduction (though preparatively rather than catalytically) of ruthenium trichloride in his preparation of trans-[Ru(py)4Cl2][H(ONO2)2]
  92. 92.
    R. D. Gillard and P. R. Mitchell, ‘Tris(diamine)chromium(III) Salts’, in “Inorganic Syntheses”, ed. F. A. Cotton, Vol. 13, McGraw-Hill Inc, New York, USA, 1972, p. 184–186 LINK https://doi.org/10.1002/9780470132449.ch38
  93. 93.
    N. Tanaka and K. Nagase, Bull. Chem. Soc. Japan, 1967, 40, (3), 546–550 LINK https://doi.org/10.1246/bcsj.40.546
  94. 94.
    N. Serpone and F. Bolletta, Inorg. Chim. Acta, 1983, 75, 189–192 LINK https://doi.org/10.1016/S0020-1693(00)91211-8
  95. 95.
    D. P. Rillema, J. F. Endicott and J. R. Barber, J. Am. Chem. Soc., 1973, 95, (21), 6987–6992 LINK https://doi.org/10.1021/ja00802a019
  96. 96.
    A. G. Beaumont and R. D. Gillard, J. Chem. Soc . A, 1968, 2400–2403 LINK https://doi.org/10.1039/J19680002400
  97. 97.
    G. T. Morgan and J. D. Main-Smith, J. Chem. Soc., 1922, 121, 1956–1971 LINK https://doi.org/10.1039/CT9222101956
  98. 98.
    G. T. Morgan and J. D. Main-Smith, J. Chem. Soc., 1924, 125, 1996–2004 LINK https://doi.org/10.1039/CT9242501996
  99. 99.
    Y. Yamamoto, K. Ito, H. Yoneda and M. Mori, Bull. Chem. Soc. Japan, 1967, 40, (11), 2580–2583 LINK https://doi.org/10.1246/bcsj.40.2580
  100. 100.
    C. D. Lawrence and C. F. H. Tipper, J. Chem. Soc., 1955, 713–716 LINK https://doi.org/10.1039/JR9550000713
  101. 101.
    C. F. H. Tipper, J. Chem. Soc., 1955, 2045–2046
  102. 102.
    D. M. Adams, J. Chatt, R. G. Guy and N. Sheppard, J. Chem. Soc., 1961, 738–742 LINK https://doi.org/10.1039/JR9610000738
  103. 103.
    S. E. Binns, R. H. Cragg, R. D. Gillard, B. T. Heaton and M. F. Pilbrow, J. Chem. Soc. A, 1969, 1227–1231 LINK https://doi.org/10.1039/J19690001227
  104. 104.
    R. H. Dainty later did extensive work on the effects of bacteria on meats at the Norwegian Food Research Institute
  105. 105.
    C. Thorpe went on to work at Department of Chemistry and Biochemistry in the University of Delaware
  106. 106.
    S. H. Laurie, whose PhD work at Aberystwyth with C. B. Monk contributed experience in the field of interactions of ligands with metal ions; subsequently he worked at Leicester Polytechnic (later De Montfort University) until his retirement
  107. 107.
    E. Beccari, Boll. Soc. Ital. Biol. Sper., 1938, 13, 6–8
  108. 108.
    E. Beccari, Boll. Soc. Ital. Biol. Sper., 1938, 13, 8–11
  109. 109.
    E. Beccari, Boll. Soc. Ital. Biol. Sper., 1941, 16, 214–216
  110. 110.
    E. Beccari, Boll. Soc. Ital. Biol. Sper., 1941, 16, 216–218
  111. 111.
    E. Beccari, Arch. Sci. Biol. (Bologna), 1941, 27, 204–246
  112. 112.
    Francis Patrick John (Frank) Dwyer (1910–1962) was an important and influential Australian chemist, one of the pioneers of bioinorganic chemistry. He mentored most of the following generation of Australian inorganic chemists, including e.g. R. S. Nyholm, A. M. Sargeson and B. Bosnich. The last-named provides a link between Dwyer’s seminal work on metal complexes in bio-systems with Gillard’s research on such topics as bacterial growth (cf. the series “Coordination Compounds and Micro-Organisms” –see Table S5) (113–115). Dwyer’s contribution to this field was outlined many years later in (116) and subsequently detailed in (117)
  113. 113.
    F. P. Dwyer, E. C. Gyarfas, W. P. Rogers and J. H. Koch, Nature, 1952, 170, (4318), 190–191 LINK https://doi.org/10.1038/170190a0
  114. 114.
    W. W. Brandt, F. P. Dwyer and E. C. Gyarfas, Chem. Rev., 1954, 54, (6), 959–1017 LINK https://doi.org/10.1021/cr60172a003
  115. 115.
    F. P. Dwyer, E. C. Gyarfas, R. D. Wright and A. Shulman, Nature, 1957, 179, (4556), 425–426 LINK https://doi.org/10.1038/179425a0
  116. 116.
    E. Meggers, Curr. Opin. Chem. Biol., 2007, 11, (3), 287–292 LINK https://doi.org/10.1016/j.cbpa.2007.05.013
  117. 117.
    N. L. Kilah and E. Meggers, Aust. J. Chem., 2012, 65, (9), 1325–1332 LINK https://doi.org/10.1071/CH12275
  118. 118.
    A. Shulman, G. M. Laycock, E. J. Ariëns and A. R. H. Wigmans, Eur. J. Pharmacol., 1970, 9, (3), 347–357 LINK https://doi.org/10.1016/0014-2999(70)90234-7
  119. 119.
    H. M. Butler, J. C. Laver, A. Shulman and R. D. Wright, Med. J. Aust., 1970, 2, (7), 309–314 LINK https://doi.org/10.5694/j.1326-5377.1970.tb50012.x
  120. 120.
    A. Shulman and D. O. White, Chemico-Biol. Interact., 1973, 6, (6), 407–413 LINK https://doi.org/10.1016/0009-2797(73)90060-4
  121. 121.
    B. Rosenberg, L. Van Camp and T. Krigas, Nature, 1965, 205, (4972), 698–699 LINK https://doi.org/10.1038/205698a0
  122. 122.
    B. Rosenberg, L. Van Camp, E. B. Grimley and A. J. Thomson, J. Biol. Chem., 1967, 242, (6), 1347–1352 LINK https://www.jbc.org/content/242/6/1347.long
  123. 123.
    R. J. Bromfield, R. H. Dainty, R. D. Gillard and B. T. Heaton, Nature, 1969, 223, (5207), 735–736 LINK https://doi.org/10.1038/223735a0
  124. 124.
    R. D. Gillard, J. D. Pedrosa de Jesus and A. Y. A. Mohamed, Trans. Met. Chem., 1989, 14, (4), 258–260 LINK https://doi.org/10.1007/BF01098223
  125. 125.
    F. P. Dwyer, I. K. Reid, A. Shulman, G. M. Laycock and S. Dixson, Aust. J. Exp. Biol. Med. Sci., 1969, 47, (2), 203–218 LINK https://doi.org/10.1038/icb.1969.21
  126. 126.
    H. Grossman, A. Shulman and C. Bell, Experientia, 1973, 29, (12), 1522–1524 LINK https://doi.org/10.1007/BF01943893
  127. 127.
    The effects of these complexes on the in vitro growth of a range of bacteria were studied. Only trans-[RhL4X2]+, where L = a pyridine and X = chloride or bromide, showed usefully high levels of antibacterial activity, with bromide complexes being about ten times more effective than their chloride analogues. At very low concentrations these rhodium complexes lead to filamentous growth of Escherichia coli, recalling the seminal experiments of Rosenberg’s group using cis-[PtCl4(NH3)2]cf. (121, 122)
  128. 128.
    W. P. Griffith, Platinum Metals Rev., 2013, 57, (2), 110–116 LINK https://www.technology.matthey.com/article/57/2/110-116/
  129. 129.
    R. D. Gillard, ‘Rhodium Complexes and Bacteria’, 1st International Conference on the Chemistry of the Platinum Group Metals, 19th–24th July, 1981, Bristol, UK, Royal Society of Chemistry, London, UK, Abstract A8
  130. 130.
    (131) describes the preparation and characterisation of enantiomers and a racemate of trans-[Rh(nicH)4Cl2](PF6)5, while (132) reports on the biological activities of these complexes
  131. 131.
    R. D. Gillard and E. Lekkas, Trans. Met. Chem., 2000, 25, (6), 617–621 LINK https://doi.org/10.1023/A:1007088115719
  132. 132.
    R. D. Gillard and E. Lekkas, Trans. Met. Chem., 2000, 25, (6), 622–625 LINK https://doi.org/10.1023/A:1007040232557
  133. 133.
    R. D. Gillard, Platinum Metals Rev., 1970, 14, (2), 50–53 LINK https://www.technology.matthey.com/article/14/2/50-53/
  134. 134.
    U. Ndagi, N. Mhlongo and M. E. Soliman, Drug Des., Dev. Ther., 2017, 11, 599–616 LINK https://doi.org/10.2147/DDDT.S119488
  135. 135.
    J.-J. Zhang, J. K. Muenzner, M. A. Abu El Maaty, B. Karge, R. Schobert, S. Wölfl and I. Ott, Dalton Trans., 2016, 45, (33), 13161–13168 LINK https://doi.org/10.1039/C6DT02025A
  136. 136.
    R. D. Gillard and S. H. Laurie, ‘Metal-Protein Interactions’, in “Biochemistry of Food Proteins”, ed. B. J. F. Hudson, Ch. 5, Springer Science and Business Media, Dordrecht, The Netherlands, 1992, pp. 155–196 LINK https://doi.org/10.1007/978-1-4684-9895-0_5
  137. 137.
    I. J. Ellison and R. D. Gillard, J. Chem. Soc., Chem. Commun., 1992, (11), 851–853 LINK https://doi.org/10.1039/C39920000851
  138. 138.
    Pages 56–69 of (139) list actual and proposed rhodium(IV), (V) and (VI) compounds and complexes (as of 1982); pages 60 and 64 are the most relevant to Gillard’s work in this area
  139. 139.
    D. J. Gulliver and W. Levason, Coord. Chem. Rev., 1982, 46, 1–127 LINK https://doi.org/10.1016/0010-8545(82)85001-7
  140. 140.
    However, Cs2RhCl6 is, as one might expect, a Rh(IV) compound – see (141) – as are several other M2RhX6 salts and the binary halides RhF4 and RhCl4 (see (142, 143)) RhO2 is also known –see (144) and references therein
  141. 141.
    I. J. Ellison and R. D. Gillard, Polyhedron, 1996, 15, (2), 339–348 LINK https://doi.org/10.1016/0277-5387(95)96713-W
  142. 142.
    W. P. Griffith, “The Chemistry of the Rarer Platinum Metals (Os, Ru, Ir and Rh)”, Wiley Interscience, London, UK, 1967, pp. 317–318
  143. 143.
    S. A. Cotton, ‘Rhodium and Iridium: Halides and Halide Complexes: Iridium Halides’, in “Chemistry of Precious Metals”, Ch. 2, Chapman and Hall, London, UK, 1997, p. 80
  144. 144.
    E. M. Miguelez, M. A. A. Franco and J. Soria, J. Solid State Chem., 1983, 46, (2), 156–161 LINK https://doi.org/10.1016/0022-4596(83)90136-6
  145. 145.
    C. Claus, “Beiträge zur Chemie der Platinmetalle”, Festschrift zur Jubelfeier des 50-Bestehens der Universität Kazan, Dorpat, 1854 LINK https://doi.org/10.1002/jlac.18470630306
  146. 146.
    C. Claus, J. Prakt. Chem., 1860, 80, (1), 282–317 LINK https://doi.org/10.1002/prac.18600800129
  147. 147.
    C. Claus, Bull. Acad. Imp. Sci. Saint-Pétersbourg, 1860, 2, 158–188 LINK https://www.biodiversitylibrary.org/item/104584#page/452/mode/1up
  148. 148.
    The blue colour eventually generated by reaction with hypochlorite solution was used in the late 19th century as a test for rhodium –see, for example (149)
  149. 149.
    E. Demarçay, Comptes Rendus, 1885, 101, 951–952 LINK https://www.biodiversitylibrary.org/item/23718#page/957/mode/1up
  150. 150.
    P. Poulenc and G. Ciepka, ‘Rhodium’, in “Nouveau Traité de Chimie Minérale”, ed. P. Pascal, Vol. 19, Masson, Paris, France, 1958, pp. 353–355
  151. 151.
    A. N. Buckley, J. A. Busby, I. J. Ellison and R. D. Gillard, Polyhedron, 1993, 12, (2), 247–253 LINK https://doi.org/10.1016/S0277-5387(00)81634-4
  152. 152.
    Mann studied a series of Lifschitz salts derived from unsymmetrical aliphatic diamines in an attempt to determine whether the nickel was in a square-planar or a tetrahedral environment. His failure to obtain any evidence for the existence of cis and trans isomers favoured tetrahedral stereochemistry at the metal centre –see (153)
  153. 153.
    F. G. Mann, J. Chem. Soc., 1927, 2904–2918 LINK https://doi.org/10.1039/JR9270002904
  154. 154.
    I. Lifschitz, J. G. Bos and K. M. Dijkema, Z. Anorg. Allg. Chem., 1939, 242, (2), 97–116 LINK https://doi.org/10.1002/zaac.19392420201
  155. 155.
    I. Lifschitz and J. G. Bos, Rec. Trav. Chim. Pays Bas, 1940, 59, (5), 407–422 LINK https://doi.org/10.1002/recl.19400590502
  156. 156.
    I. Lifschitz and K. M. Dijkema, Rec. Trav. Chim. Pays Bas, 1941, 60, (8), 581–598 LINK https://doi.org/10.1002/recl.19410600803
  157. 157.
    H. Glaser and P. Pfeiffer, J. Prakt. Chem., 1939, 153, (10–12), 300–312 LINK https://doi.org/10.1002/prac.19391531005
  158. 158.
    D. M. L. Goodgame and L. M. Venanzi, J. Chem. Soc., 1963, 616–627 LINK https://doi.org/10.1039/JR9630000616
  159. 159.
    D. M. L. Goodgame and L. M. Venanzi, J. Chem. Soc., 1963, 5909–5916 LINK https://doi.org/10.1039/JR9630005909
  160. 160.
    W. C. E. Higginson, S. C. Nyburg and J. S. Wood, Inorg. Chem., 1964, 3, (4), 463–467 LINK https://doi.org/10.1021/ic50014a001
  161. 161.
    S. C. Nyburg and J. S. Wood, Inorg. Chem., 1964, 3, (4), 468–476 LINK https://doi.org/10.1021/ic50014a002
  162. 162.
    R. D. Gillard and H. M. Sutton, J. Chem. Soc. D., 1969, (16), 937–938 LINK https://doi.org/10.1039/C29690000937
  163. 163.
    R. D. Gillard and H. M. Sutton, J. Chem. Soc. A, 1970, 1309–1312 LINK https://doi.org/10.1039/J19700001309
  164. 164.
    R. D. Gillard and H. M. Sutton, J. Chem. Soc. A, 1970, 2172–2174 LINK https://doi.org/10.1039/J19700002172
  165. 165.
    R. D. Gillard and H. M. Sutton, J. Chem. Soc. A, 1970, 2175–2176 LINK https://doi.org/10.1039/J19700002175
  166. 166.
    M. J. Blandamer, D. E. Clarke, T. A. Claxton, M. F. Fox, N. J. Hidden, J. Oakes, M. C. R. Symons, G. S. P. Verma and M. J. Wootten, Chem. Commun. (London), 1967, (6), 273–274 LINK https://doi.org/10.1039/C19670000273
  167. 167.
    M. J. Barcelona and G. Davies, J. Chem. Soc., Dalton Trans., 1975, (19), 1906–1909 LINK https://doi.org/10.1039/DT9750001906
  168. 168.
    Several years earlier Gillard had described synergic solubility behaviour for the rhodium complex [RhCl(py)3(C2O4)]in water + pyridine mixtures, where the complex is much more soluble (up to approximately 30 times) than in either solvent –see (169). He revisited synergic solubility towards the end of his career, this time in relation to the iridium analogue [IrCl(py)3(C2O4)] again in water + pyridine mixtures (170)
  169. 169.
    R. D. Gillard, E. D. McKenzie and M. D. Ross, J. Inorg. Nucl. Chem., 1966, 28, (6–7), 1429–1434 LINK https://doi.org/10.1016/0022-1902(66)80175-6
  170. 170.
    N. S. A. Edwards, R. D. Gillard, M. B. Hursthouse, H. F. Lieberman and K. M. A. Malik, Polyhedron, 1993, 12, (24), 2925–2928 LINK https://doi.org/10.1016/S0277-5387(00)80040-6
  171. 171.
    R. D. Gillard, Trans. Met. Chem., 1989, 14, (4), 295–297 LINK https://doi.org/10.1007/BF01098233
  172. 172.
    H. O. Davies, J.-H. Park and R. D. Gillard, Inorg. Chim. Acta, 2003, 356, 69–84 LINK https://doi.org/10.1016/S0020-1693(03)00402-X
  173. 173.
    For example, the characterisation of Hg2[Ni(SCN)6]·H2O and Ni[Hg(SCN)4]·2H2O in the nickel(II)–mercury(II)–thiocyanate system (174), whose components had been a matter for discussion since the 1860s (175, 176)
  174. 174.
    R. D. Gillard and M. V. Twigg, Inorg. Chim. Acta, 1972, 6, 150–152 LINK https://doi.org/10.1016/S0020-1693(00)91775-4
  175. 175.
    P. T. Cleve, Öefersigt. Kongl. Veten.-Akad. Förhandl., 1863, 20, 9–13 LINK https://www.biodiversitylibrary.org/item/100846#page/19/mode/1up
  176. 176.
    P. T. Cleve, J. Prakt. Chem., 1864, 91, 227–228 LINK https://doi.org/10.1002/prac.18640910140

4. Acknowledgements

Many people provided information and reminiscences about Gillard and a full list appears at the end of the second part of this commemoration. Those who provided photographs are acknowledged in the accompanying caption.

5. Supplementary Material

The following Tables may be found in the Supplementary Information included with the online version of this article:

Table S1 Publications in the Series “Adducts of Coordination Compounds”

Table S2 The First Seven and Final Two Publications in the Series “Optically-active Coordination Compounds”

Table S3 Publications in the Series “Isomers of α-Amino acids with Copper(II)”

Table S4 Publications in the Series “Reactions of Complex Compounds of Cobalt”

Table S5 Publications in the Series “Coordination Compounds and Micro-organisms”

Table S6 Papers Published in the Series “Oxidants Containing Rhodium”

Table S7 The Series “Metal Complexes as Indicators for Solvent Structure”

Table S8 The Series “Sulphides of the Platinum Group Elements”

Table S9 The First Six and Last Four Publications, Plus Intervening PGM-Relevant Papers, of the Series “Equilibria in Complexes of N-Heterocyclic Molecules”

Table S10 Publications Concerned with Medical Aspects, Mobilisation of Aluminium from Cookware and Accumulation of Aluminium by Tea Plants Which Led to Gillard’s Article “Beware The Cups That Cheer”

Table S11 The Series “Oxovanadium(IV) – Amino-Acids”

Table S12 Reports on Conference Proceedings in the Journal of Inorganic Biochemistry Related to the Series “Oxovanadium(IV) – Amino-Acids”

Download the Supplementary Information (PDF, 394 KB)

The Authors


After grammar school (Queen Elizabeth’s, Barnet), National Service (Royal Artillery), and Cambridge (Sidney Sussex; MA, PhD on inorganic kinetics) John Burgess started work at Fisons Fertilizers in Suffolk. Two years later he embarked on an ICI Fellowship at the University of Leicester which led to three decades of teaching and research – ranging from mechanisms to solvatochromism to biochemistry, linked by solution chemistry of iron complexes. He is now Emeritus Reader in Inorganic Chemistry at the University of Leicester, combining the preparation of an expanded version of “Color of Metal Compounds” with gardening and pursuing his interests in music, East Anglian churches and railways.


Martyn Twigg did inorganic reaction mechanisms graduate research in a laboratory next to Gillard’s office at Canterbury. After fellowships at Toronto and Cambridge and being headhunted into the ICI Corporate Laboratory he moved to ICI Billingham to work on industrial process catalysts. Later at Johnson Matthey he was responsible for autocatalyst development and production at Royston. After emissions control successes he retired in 2010 and continues research with universities in the UK and overseas with honorary positions at some. His catalyst development, manufacturing and consulting business is thriving with novel catalytic systems in production.

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