Modern Coordination Chemistry

The Legacy of Joseph Chatt

By G. J. Leigh, N. Winterton

The Royal Society of Chemistry

Copyright © 2002 The Royal Society of Chemistry
All rights reserved.
ISBN: 978-0-85404-469-6

Contents

Abbreviations, xxvi,
Section A: Reminiscences of Joseph Chatt Drawn from Conversations and from the Recollections of Co-workers, 1,
Section B: Recent Developments in the Synthesis, Bonding Modes and Reactivity of Hydrido and Dihydrogen Complexes, 29,
Section C: The Chemistry of Phosphines, 67,
Section D: Transition Metal Complexes of Olefins, Acetylenes, Arenes and Related Isolobal Ligands, 101,
Section E: Chemistry Related to Dinitrogen Complexes, 169,
Section F: The Biological Work of the ARC Unit of Nitrogen Fixation at the University of Sussex, and Later Developments, 231,
Section G: Patterns and Generalisations in Stability and Reactivity, 303,
Section H: Other Papers Presented at the 34th International Conference on Coordination Chemistry, Edinburgh, Scotland, July 2000, 341,
Index of People and Places, 375,
Subject Index, 379,

CHAPTER 1

SECTION A:

Reminiscences of Joseph Chatt Drawn from Conversations and from the Recollections of Co-workers

Joseph Chatt worked in several different establishments during his career, and he has also given an account of his early life in a recorded conversation. Clearly he was very fondly regarded by those with whom he worked, and they continue to regard their time with him as a high point in their careers. To provide a background against which those who did not know him might wish to assess his life and work, we decided to ask some of those involved to write an account of their experiences working in the Chatt group. None of those approached needed any encouragement, and their contributions are presented in this section with only very light editing to avoid excessive overlap.

[A Memoir of Joseph Chatt

G. J. LEIGH

School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton BN1 9QJ, UK

Joseph Chatt was born in the North East of England at Hordern, County Durham, on November 6, 1914. However, most of his early life was spent in the North West, in Cumberland. He once mentioned that, together with his father, he had observed German warships bombarding Hartlepool, though he must have been very young when that occurred, which was during the First World War. Nevertheless, he did have a fine memory, and his knowledge of the fundamental facts of inorganic chemistry was one of his great strengths. He had an almost personal understanding of the chemistry of the metallic elements, and his comments and advice on chemistry were generally sound, even when he could not explain why he had made them. His understanding was intuitive and inspirational, and though he was not afraid to admit he was wrong or even that he had made mistakes, everything he published was prepared with the utmost care and circumspection, often to the annoyance of his less patient and meticulous collaborators.

He inherited many of those qualities that are often regarded as characteristic of the northern Englishman. He was hard working, meticulous, blunt and honest. He was also very determined, and shrewd in his evaluation of people, even if he also had some related prejudices. He only slowly came to accept that women might also become good researchers, and he had a strong suspicion of men who sported beards. However, he could be persuaded by a demonstration of scientific ability, even if his initial reaction to some people was less than favourable. What sometimes inhibited his relationship with younger researchers, especially graduate students, was his unquestioning assumption that everyone in the laboratory had his interest in chemistry and also his enormous accumulation of knowledge. We, his colleagues, always called him Joseph, even after he retired. It was generally only colleagues from the United States who presumed to call him Joe.

Whatever he undertook to do he did with great thoroughness, whether it was chemistry or not. At one time he was interested in antique furniture, and I can recall being lectured on how to determine the age of a chair by examining the construction of the seat. This was intended to help me in my purchase of furniture for a newly acquired house, though there was little enough money to spare on any furniture, let alone on antiques. He was actually very self-centred and rather insensitive, though certainly not mean. It was always necessary to ask him for help if you required it, because he was seldom aware that it might be necessary. However, once he was asked for help he always did his utmost to assist.

He was an avid collector of coins from his youth, and specialised in English and British Empire and Commonwealth coins. He had sets of Maundy money from every English (British) sovereign who had issued such coins. At his death he was working on a catalogue of Peace Medals, medals that were struck in towns all over Britain to celebrate the end of the First World War, but which had never been listed.

He was also very lucky. This showed not only in his career and perhaps in his chemical intuition, but also, sometimes, in his hobbies. He once bought a jardinière at a sale in aid of Sussex churches. It was said to be Sevres, and it was not expensive. Subsequently he decided to take it to the Victoria and Albert Museum in London, to confirm that it was an imitation and not really a Sevres product. The curator initially agreed that it could not be genuine, so Joseph asked to be shown the Museum collection, which, of course, consists only of genuine items. As they proceeded to inspect the display, starting at the later and moving to the earlier, Joseph’s jardinière resembled more and more the Museum items, and finally the curator had to admit that the jardinière was a genuine and very rare early Sevres piece, and certainly worth much more than he had paid for it.

When he was ten years old his family moved to a farm in Cumberland, at Welton, just south of Carlisle, and there began a formative time in his development. The farm was eventually inherited by his brother, and Joseph never became a farmer, even though the agriculturally pertinent topic of nitrogen fixation ultimately became his major professional interest. He enjoyed fell-walking and cycling, and was clearly very active. During this time he sustained damage to his leg that left him semi-crippled, though it was only towards the end of his life that he was forced to use a stick as well as special shoes and a leg-iron.

Cumbria and the Lake District are heavily mineralised, and the abundance of minerals in the rocks all around his home stimulated his interest in chemistry and also in exploring the hills. In this he was also aided by his uncle who was Chief Chemist in a steel works in Newcastle-upon-Tyne. The young Joseph visited him often and was given the run of the analytical laboratory. It was during this time that he developed a very refined experimental technique and also an interest in experimentation generally. Joseph learned how to make working models in glass of Hero’s engine, starting with glass tubing. This required considerable skill, even more so when one realises that he must have been obliged to use soda glass. Until quite late in his career he required a bench to be kept in the lab for his particular use, though he seldom had the time to indulge himself in laboratory work.

Encouraged by learning that the Romans had once found gold in the Lake District, Joseph hunted for it in the fells around the family farm, though for once he appears to have been unsuccessful. He set up a lighting system based on a dichromate cell in his bedroom, the control being the raising of an electrode from the acid bath using a piece of string. At that time one could buy chemicals from the local chemist (pharmacist) and the young Chatt was able to purchase things such as metallic sodium and aqua regia. He once claimed that he was one of the very few people to have observed the reaction of metallic sodium with aqua regia, and one would not wish to query this claim! It seems to have been rather spectacular. Somewhat later the destruction of some more of his sodium metal by throwing it into the water at Silloth Dock on the Cumbrian coast led to reports that the port had suffered an IRA attack, and apparently these have never been corrected. This story is told in detail elsewhere (G. J. Leigh, Coord. Chem. Rev., 1991, 108, 4), but Joseph was hesitant to publish the true details even in 1991, some fifty years after the event.

Joseph’s family was not academic, and his father did not understand how the education system functioned at that time. Consequently, Joseph remained at the village school until he was fourteen. It is apparent that the family was never very flush with money, and spending some on educating a child beyond the minimum legal age in a private establishment required a considerable sacrifice. Nevertheless, at the age of fourteen he was admitted to the Nelson School in nearby Wigton, for which the normal age of entry was eleven. His promise was very quickly recognised, and he was given every encouragement by several of the teachers, some of whom are named in the above reference. As well as receiving local scholarships for financial support, he was given specific help with his mineralogy and chemistry, and he matriculated within two years instead of the usual four. Matriculation is a term no longer used, but it was then a qualification obtained at the age of fifteen or so, and was a necessary preliminary requirement for further study at a university.

Chatt’s arrival at Cambridge owed everything to the mathematics master at the Nelson School. He thought that Joseph would benefit even more from Cambridge than he would from studying at Durham, which had been the original plan, and so in the late summer of 1935 Mr Burns went to Cambridge to try to encourage his own old college, St John’s, to admit this promising young man who had already achieved so much and had already won at least two scholarships. The college was full, so he tried others, finally asking at Emmanuel College. They were also full, but the admissions tutor said that they generally lost a potential student ‘falling down an Alp or something, in the long vacation’. So Joseph was given a place, on the understanding that he would obtain the required qualification in Latin, which was at that time regarded as an indispensable part of every person’s University education. This he did in very short time, and he graduated in the summer of 1937.

He carried on with graduate work with F. G. Mann, for whom he always had the highest personal and scientific regard. Mann was one of those few pioneers who persisted with inorganic chemistry throughout the 1920s and 1930s, at which time inorganic chemistry was generally believed to have been finished and exhausted, and of no further interest. Mann wished to prepare organophosphine complexes of transition elements, because phosphines were known to produce low-melting adducts with transition-metal salts and these adducts could be used to measure parachors. The parachor was expected to give information about the nature of the coordinate bond, and these two directions, phosphines and the coordinate bond, were to inform much of Chatt’s earlier work at The Frythe (see below, pp. 8, 11, 18 and 25). Joseph’s first six papers, published jointly with Mann, concerned phosphines and arsines and their complexes with elements such as palladium. The platinum metals also became an area of early interest.

Chatt graduated when the Second World War was beginning, and he was drafted immediately into work for the war effort. Because 1,3-dinitrobenzene proved to be a better explosive than had been expected, it was felt (apparently originally by Sir Robert Robinson) that 1,3,5,7-tetranitronaphthalene might be exceptionally good. There are 24 tetranitronaphthalenes, and Joseph was asked to make 200 g of this particular isomer in the Cambridge University laboratory. Unfortunately, the eight months’ effort he needed to produce the compound were wasted as the compound proved to be a very disappointing explosive. In truth, the Ministry of Works, his then employer, had little idea of what a man of Chatt’s calibre might achieve and a little later they were reasonably happy to let him resign. He took up employment with Peter Spence and Sons Ltd at Widnes, where he worked on various war-related projects such as the reduction of titanium tetrachloride to give aqueous titanium trichloride and the properties of activated alumina. He ultimately became Chief Chemist. Even then, he pursued his own private researches on olefin complexes in his spare time. It was at Widnes that he met his future wife, Ethel Williams.

Joseph had originally planned to pursue an academic career, and had even arranged to teach heterocyclic chemistry at St Andrews, but the war had put a stop to that. Once the war had ended he decided to try academe once more, and finally took up an appointment in inorganic chemistry at Imperial College. He found the life and the facilities at Imperial College completely unsatisfying. He was not able to do any research work, and to the end of his life he never really ever believed that a university chemistry department was the best place to do chemistry research. Afterwards, at the ICI laboratory at The Frythe and later, in the Nitrogen Fixation Unit at Sussex, he made great efforts to ensure that everyone realised that research was the prime and only significant activity of the laboratory, and that every person and thing in the organisation should operate in order to make the research as fruitful as possible. He was extremely successful, and his students and collaborators have carried the message across the world.

As a result of the frustrations he experienced at Imperial College, Chatt decided to go back to industry, and approached Dr R. M. Winter, who was then Controller of Research at ICI, for a job. As a result, he was appointed to a position at the ICI Butterwick Research laboratories at The Frythe, a large country house, near Welwyn Garden City. These laboratories were intended by ICI to be for fundamental research. After some local in-fighting, Chatt obtained the separate inorganic department he had been promised. With himself and just a single assistant he started what was probably the most productive period of his research career. Personal accounts of that period and the subsequent work at the Unit of Nitrogen Fixation and the University of Sussex are to be found elsewhere in this book.

After his formal retirement from the Unit of Nitrogen Fixation in 1980, he moved his office into the then School of Chemistry and Molecular Science at the University of Sussex. He continued to pursue research, though he found it difficult to maintain his degree of productivity without the permanent professional support provided in the Unit. He was still a regular attender at chemistry seminars, and his understanding and insights were as keen as ever, even if his knowledge was becoming a little dated. He still enjoyed travelling, especially sea cruises, and had taken up painting. He was particularly pleased when, unexpectedly, someone bought one of his paintings at an exhibition. He was in reasonable health for his age, and supported his wife in her activities in local art societies.

Joseph died suddenly on May 19, 1994, whilst preparing himself for a joint photograph with the six Fellows of the Royal Society who were then working in chemistry at the University of Sussex. The sadness at his passing was tempered by the realisation that he had led a long, full and rewarding life, and had enriched the world of chemistry by his discoveries and example, perhaps by more than any of his contemporaries.

A Memorable Start to a Career

RALPH G. WILKINS

Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM 88003-8001, USA

In September 1949, I was just completing a PhD supervised by Richard Burkin, at University College, Southampton, examining the coordination chemistry of copper(I) complexes of long-chain aliphatic amines. As luck would have it, a position tailor-made for me had become available at the ICI Butterwick Research Laboratories in Welwyn. The work would involve fundamental research in a small group headed by Dr J. Chatt. I knew of his work with F. G. Mann at Cambridge before the war, and after an interview, I was delighted and not a little surprised, to be offered the position, which I accepted with alacrity! Years later, Joseph told me that my enthusiasm had won the day over some stiff opposition, which says more about him than about me.

The inorganic chemistry group headed by Dr Chatt consisted of Alan Williams and Alan Hart who were working towards degrees, and I was therefore the first of many graduates to join him. We were housed in a small building (hut might be a better description) of which there were many in the grounds of a Victorian mansion, The Frythe. It is appropriate here to say something about the establishment. There were a number of research groups. As well as inorganic, some others that I recall were organic, physical, microbiology and toxicology. My memory may be a little hazy about these and other matters! Most of us lived on-site in small huts, each housing a few people, and we were fed quite well in the main house. Some of the (mainly senior) scientists travelled from London daily and were picked up at Welwyn Garden City station. Joseph and Ethel Chatt had a house in St Albans.

It was a wonderful environment in which to get to know other scientists in different disciplines. I remember particularly the organic chemists who were working on the antibiotic griseofulvin. Some of these were John Grove, Jake Macmillan and Dunc (L. A. Duncanson, who was to enjoy a very fruitful collaboration with the inorganic group). There were ‘relevant’ overtones to our researches, but a fundamental approach was encouraged.

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