From: Eric J. Leopold (ejlmp$##$earthlink.net)
Date: Sat Apr 21 2001 - 06:21:58 EDT
Thanks Ashutosh for the story of Woodward but here's a more readable
>To: Multiple recipients of list orglist <orglist$##$dq.fct.unl.pt>
>From: "Ashutosh" <ashujo$##$yahoo.com>
>Subject: ORGLIST: Of sandwiches and Nobel Prizes
>Date: Thu, 19 Apr 2001 13:54:03 +0530
>A fascinating story of how R. B. Woodward did not win the Nobel
>Prize of 1973, with Geofferey Wilkinson and E. O. Fischer,... and
>why he should have.
>The Northeastern Section of the American Chemical Society
>Of Sandwiches and Nobel Prizes:
>Robert Burns Woodward
>By Thomas M . Zydowsky, Worcester, MA*
>The notice in The Times of London (October 24; p. 5) of the award of
>this year's Nobel Prize in Chemistry leaves me no choice but to let
>you know, most respectfully, that you have inadvertently, I am sure
>committed a grave injustice."
>Letter From R.B. Woodward To The Nobel Committee For Chemistry,
>Dated October 26, 1973.
>Ernst O. Fischer and Geoffrey Wilkinson received the 1973 Nobel
>Prize in chemistry for their pioneering work, performed
>independently, on the chemistry of the organometallic sandwich
>compounds.1 The decision to award the Nobel Prize to Fischer and
>Wilkinson was hardly questioned, since it was a fitting tribute to
>their extensive, groundbreaking efforts over the preceding two
>decades. However, the decision not to award a share of the Nobel
>Prize to Robert Burns Woodward was questioned, and even after 25
>years, it continues to be a sensitive and emotional issue in some
>Perhaps Woodward himself provided the most emotional and
>historically significant response to the 1973 Nobel Prize. His
>public response varied, but in many situations he said little, if
>anything, about the prize.3 His recently discovered private
>response, which he mailed to the Nobel Committee for Chemistry two
>days after the winners of the 1973 Nobel Prize were announced,
>reflected his intense desire to receive credit for his seminal
>contributions to organometallic sandwich chemistry.4
>We must examine events from 1952 to understand Woodward's reaction
>to the 1973 Nobel Prize in chemistry. In late 1951 and early 1952,
>two independent research groups published papers describing the
>synthesis of an unusually stable iron-containing compound: Kealy and
>Pauson from Duquesne University published a paper entitled A New
>Type of Organo-Iron Compound,5 and Miller, Tebboth, and Tremaine
>from The British Oxygen Company published a paper entitled
>Kealy and Pauson's paper was submitted to Nature on August 7, 1951,
>published in England on December 15, 1951, and arrived in the United
>States about one month later. Miller, Tebboth, and Tremaine's paper
>was submitted to the Journal of the Chemical Society on July
>11,1951, published in England on March 24, 1952, and arrived in the
>United States about four to six weeks later.
>The two papers described the serendipitous synthesis, preliminary
>chemical characterization, and tentative structure assignment for
>dicyclopentadienyliron (see fig. 1). The Duquesne group discovered
>[Fig. 1 about here]
>synthesis while trying to prepare dihydrofulvalene from ferric
>chloride and cyclopentadienyl-magnesium bromide, whereas the London
>group uncovered their route during attempts to synthesize amines by
>reacting nitrogen and cyclopentadiene over iron filings. Both groups
>assigned the linear structure shown in Fig. 1 to their unexpected
>product. In doing so, they promptly attracted a contingent of
>chemists who questioned the veracity of the linear structure.
>Harvard colleagues Geoffrey Wilkinson and Robert Burns Woodward were
>part of that contingent. In 1952 Wilkinson was a first-year
>assistant professor of inorganic chemistry, and Woodward was a full
>professor of organic chemistry. Wilkinson (1921-1997) had received
>his Ph.D. in nuclear chemistry from Imperial College of Science and
>Technology in London in 1946, and before his appointment at Harvard,
>he had held postdoctoral fellowships at the University of California
>at Berkeley and at the Massachusetts Institute of Technology (MIT).
>While at MIT, Wilkinson switched from nuclear chemistry to inorganic
>chemistry. Woodward (1917-1979) was already an established star on
>the international chemistry scene in 1952. He had been a child
>prodigy and had received his Ph.D. from MIT at age 20. By 1952, he
>had already begun to publish some of the outstanding work in organic
>synthesis, structure elucidation, and theory that would subsequently
>earn him numerous honors, including the 1965 Nobel Prize in
>Myron Rosenblum was a graduate student in Woodward's group in 1952.
>He recalled that Woodward came into his lab one day in early January
>1952 and began to discuss Kealy and Pauson's Nature paper .
>According to Rosenblum, Woodward drew the linear structure for
>dicyclopentadienyliron on a blackboard and said that he thought that
>it was wrong. Woodward then carefully drew the now familiar sandwich
>structure for dicyclopentadienyliron (see Fig. 2) on
>[Fig. 2 about here]
>the same blackboard. Without offering any insight into his
>reasoning, he told Rosenblum: "I think that this is the right
>structure. Why don't you take a few days off from your work and make
>the compound and let's look at it." Rosenblum repeated Kealy and
>Pauson's synthesis, and on January 21, 1952, he had crystals of the
>bright orange compound ready for testing.
>At around the same time, Wilkinson had also come across Kealy and
>Pauson's Nature paper, and he independently thought up the sandwich
>structure for dicyclopentadienyliron . Through a subsequent
>conversation with Rosenblum, Wilkinson learned of Woodward's plan to
>investigate the novel compound. After discussing their mutual
>interest in the problem, Wilkinson and Woodward agreed on a series
>of experiments that would be used to verify their structure proposal.
>On April 2, 1952, less than four months after Kealy and Pauson's
>paper appeared, Wilkinson, Rosenblum, postdoctoral fellow Mark
>Whiting, and Woodward (order of authors on the paper) published a
>one-page communication in the Journal of the American Chemical
>Society describing the results of two experiments that ruled out the
>linear structure for dicyclopentadienyliron . The Harvard group
>reported that the dipole moment of dicyclopentadienyliron was
>effectively zero and that the infrared spectrum showed only one type
>of C-H bond. In place of the linear structure, the Harvard chemists
>proposed their new structure in which the iron atom was sandwiched
>between two cyclopentadienyl groups, hence the name sandwich
>compounds . The dipole moment and infrared data supported the
>sandwich structure; it is important to emphasize, however, that
>Wilkinson and Woodward dreamed up the sandwich structure for
>dicyclopentadienyliron before any synthetic work or physical
>characterization had even begun.
>Wilkinson and Woodward were not the only chemists to challenge the
>linear structure proposed for dicyclopentadienyliron. William E.
>Doering at Columbia not only questioned it, but in September 1951,
>he actually suggested the sandwich structure to Peter Pauson [11,
>12], and, somewhat later, John R. Johnson at Cornell also suggested
>the sandwich structure . W. C. Fernelius and E. O. Brimm had
>their doubts, and at their suggestion, Penn State College physicists
>Ray Pepinsky and Philip Eiland determined the molecular structure of
>dicyclopentadienyliron by using X-ray methods . Meanwhile, over
>in Germany, E. O. Fischer and W. Pfab also used X-ray methods to
>solve the structure. For Fischer, it was his first step on the way
>to the 1973 Nobel Prize in chemistry .
>Nothing like the sandwich structure had ever been seen before. In
>1952, Marshall Gates was the assistant editor of the Journal of the
>American Chemical Society, and he handled Woodward's manuscript
>submissions. In a letter to Woodward dated March 28,1952, Gates
>wrote: "We have dispatched your communication to the printers but I
>cannot help feeling that you have been at the hashish again.
>'Remarkable' seems a pallid word with which to describe this
>Wilkinson and Woodward's "remarkable" structure enticed yet another
>team of chemists to work on organometallic sandwich compounds.
>Jack Dunitz and Leslie Orgel were Research Fellows in England in
>1952, and Dunitz's account of their decision to work on
>dicyclopentadienyliron once again underscores the novelty and lure
>of the sandwich structure. In a 1992 paper celebrating the 40th
>anniversary of the discovery of ferrocene (dicyclopentadienyliron)
>, Dunitz said, "I think it is difficult today to appreciate just
>how surprising, unorthodox, even revolutionary, this structure must
>have appeared to chemists forty years ago. At any rate, I have to
>confess that my first reaction was one of extreme skepticism, if not
>plain disbelief." Dunitz came across Wilkinson and Woodward's paper
>shortly after it appeared, and according to Dunitz: "I opened the
>library copy of the JACS and came across this astonishing Harvard
>proposal: two parallel cyclopentadienyl rings with an iron atom
>sandwiched between them. I thought: what nerve these Harvard
>chemists have! To publicly put forward such a structure on such
>On his way out of the library, Dunitz ran into Orgel, and together
>they scrutinized Wilkinson and Woodward's paper. Orgel was as
>skeptical as Dunitz, so they decided to investigate the new
>compound. According to Dunitz, "We found that the compound was easy
>to prepare in crystalline form. We decided to make it and, by
>determining its crystal structure, demonstrate the incorrectness of
>the Harvard proposal."
>Dunitz and Orgel soon learned that Wilkinson and Woodward's sandwich
>structure was indeed correct . Their work also provided a novel
>explanation for the stability of this remarkable structure in terms
>of molecular orbital theory.
>Woodward also predicted that dicyclopentadienyliron was aromatic and
>that it would have properties characteristic of typical aromatic
>compounds such as benzene. Later in 1952, a follow-up paper from
>Woodward's group (Woodward, Rosenblum, and Whiting) confirmed the
>predicted aromatic properties of the new compound, and in that paper
>they also proposed the name ferrocene for dicyclopentadienyliron
>. That second communication was Woodward's penultimate paper in
>the ferrocene. series, although his group continued to work on
>sandwich compounds of other transition metals for at least two more
>Wilkinson was an assistant professor in search of research topics on
>which to build an independent career. He was undoubtedly aware of
>the significance of the new field that he had helped to create, and
>he recognized the long-term research potential of the sandwich
>compounds. Working independently of Woodward, Wilkinson published
>four ferrocene-related papers in 1952, and many more throughout his
>career. He subsequently became one of the world authorities on the
>chemistry of organometallic sandwich compounds and earned numerous
>awards for his work in that field, including the biggest prize of
>all-the Nobel Prize.
>During his Nobel Prize award address in Stockholm, Wilkinson
>described the two factors which, in 1952, had led him to propose the
>sandwich structure for ferrocene . The first factor was the
>well-known (to him) instability of transition-metal alkyls and
>aryls, and the second factor was his gut feeling, at that time
>unproved, concerning the binding scheme of several unrelated
>organometallic compounds. In 1951 Wilkinson was already thinking
>about transition-metal complexes of unsaturated ligands
>(cyclopentadienelike), so he was clearly a "prepared mind" waiting
>for the right chance (ferrocene) to come along .
>Wilkinson recounted the events leading up to his independent
>proposal of the sandwich structure in a 1975 paper . He described
>his thinking when he came across Kealy and Pauson's Nature, paper
>during his weekly visit to the departmental library in this way:
>On seeing the structure I, which was also the one Miller, Tebboth,
>and Tremaine had drawn in their paper which appeared later, I can
>remember immediately saying to myself "Jesus Christ it can't be
>that!" Now I don't know why it was not the Sedgwick view quoted
>above that first occurred to me but the chelate diene structure, but
>I remember scribbling out on a piece of paper the structure II in
>which both double bonds were coordinated, and almost immediately
>III, as the significance of the resonance structures (I had been
>much impressed by Pauling) dawned, and the equivalence of the
>carbons became obvious, "It's a sandwich." The thing that really
>excited me was the thought that if iron did this, the other
>transition metals must also form sandwich compounds.
>Wilkinson went on to say that he and Woodward independently, and for
>different chemical reasons, proposed the sandwich structure for
>dicyclopentadienyliron, and, over lunch at the Harvard Faculty Club
>one afternoon, they agreed to carry out the experiments needed to
>verify their structure proposal. He also acknowledged that Woodward
>suggested that ferrocene would behave like a typical aromatic
>compound and that he (Wilkinson) had not considered that possibility.
>Woodward was on sabbatical leave in England when the Nobel Committee
>announced the winners of the 1973 Nobel Prize in chemistry. In an
>unpublished letter to the Chairman of the Nobel Committee for
>Chemistry dated October 26, 1973, Woodward reacted to the press
>release for the 1973 Nobel Prize in chemistry in this way :
>The notice in The Times of London (October 24, p. 5) of the award of
>this year's Nobel Prize in Chemistry leaves me no choice but to let
>you know, most respectfully, that you have inadvertently, I am sure
>-- committed a grave injustice.
>Woodward went on to quote several newspaper articles that had
>described Fischer and Wilkinson's contributions to organometallic
>sandwich chemistry, especially their role in the structure
>elucidation of ferrocene. The articles stressed the novelty and
>significance of the exciting new sandwich compounds but never once
>mentioned Woodward's contributions to the ferrocene story.
>Woodward then gave his account of the events leading up to the
>proposal of the correct structure for ferrocene:
>The problem is that there were two seminal ideas in this field-first
>the proposal of the unusual and hitherto unknown sandwich structure,
>and second, the prediction that such structures would display
>unusual, "aromatic" characteristics. Both of these concepts were
>simply, completely, and entirely mine, and mine alone. Indeed, when
>I, as a gesture to a friend and junior colleague interested in
>organo-metallic chemistry, invited Professor Wilkinson to join me
>and my colleagues in the simple experiments which verified my
>structure proposal, his initial reaction to my views was close to
>derision . . . . But in the event, he had second thoughts about his
>initial scoffing view of my structural proposal and its
>consequences, and all together we published the initial seminal
>communication that was written by me. The decision to place my name
>last in the roster of authors was made, by me alone, again as a
>courtesy to a junior staff colleague of independent status.
>Wilkinson and Woodward gave vastly different accounts of their early
>contributions to organometallic sandwich chemistry. According to
>Wilkinson's 1975 account, he thought up the sandwich structure for
>ferrocene while reading Kealy and Pauson's Nature article, several
>days prior to his conversation with Woodward at the Harvard Faculty
>Club. He regarded himself as a well-trained independent investigator
>who had spent considerable time thinking about the bonding in
>transition-metal complexes and naturally claimed co-inventorship for
>the sandwich structure. He also felt that from the beginning, he and
>Woodward agreed on the new: structure, and that theirs was a
>collaborative' effort in which both parties contributed to the
>On the other hand, Woodward claimed sole inventorship for both ideas
>(sandwich structure and aromaticity). He recalled that Wilkinson
>initially derided his (Woodward's) sandwich structure proposal but
>eventually embraced the structure and its consequences. Woodward
>also stated that he did Wilkinson a favor by letting him participate
>in the experiments that verified the structure proposal and by
>putting Wilkinson as first author. Wilkinson thought he and Woodward
>were peers, whereas Woodward saw himself as the mentor and Wilkinson
>as his protégé.
>Woodward closed his letter to the Nobel Committee by saying that he
>had not seen the actual award citation issued by the Swedish Academy
>of Sciences or the official press release:
>Regrettably the precise citation issued by The Academy in connection
>with the award is not available to me here in England, nor have I
>been able to find a complete account of the ancillary material
>released to the press. Quite possibly the former does not signalize
>the special importance of the unique structural proposal and the
>demonstration of its correctness, and the latter well make a clear
>acknowledgment--ignored by the press-of my definitive contributions
>in those respects. Should these things be true--though in all candor
>I have to say that the actual press reports here provide no basis
>for supposing that they are--the problem is much minimized. But, I
>am sure that you will understand that I cannot read with equanimity
>such distorted and historically incorrect statements as those quoted
>In fact, neither the award citation nor the ancillary material
>released to the press mentioned Woodward by name. In a reply to
>Woodward's letter, Arne Fredga,-then Chairman of the Nobel Committee
>for Chemistry, wrote':
>Your letter of 26th October was received. It contains information
>not evident from the publications, but of great interest for the
>history of science . . . . The committee does not make available to
>the press information about a newly elected Nobel Laureate . . . .
>it is customary not to mention co-workers and co-authors who are not
>sharing the prize, and this rule has been followed also in the
>Woodward's letter apparently induced at least one member of the
>Nobel Committee to overlook the rule. Acting either on his own or
>with the approval of his colleagues, Professor Ingvar Lindqvist
>acknowledged Woodward's contributions on two separate occasions
>during his introduction of Fischer and Wilkinson at the 1973 Nobel
>Prize ceremony . Lindqvist said:
>The facts were available for all to see. Once the correct hypothesis
>was arrived at, by fantasy or intuition, it readily lent itself to
>simple process of logical deduction. I am of course referring to the
>way in which they, together with the former Nobel Laureate Woodward,
>reached the conclusion that certain compounds could not be
>understood without the introduction of a new concept, namely that of
>the sandwich compounds . . . . This they did by the successful
>synthesis of a large number of compounds which were analogous to the
>initially discovered ferrocene , (named by Woodward in analogy to
>benzene), but with other metals than iron . . . .
>The fact remains that Fischer and Wilkinson received the 1973 Nobel
>Prize in chemistry for their extensive investigations on the
>chemistry of organometallic sandwich compounds, not the discovery.
>Despite having a clear understanding of the importance of the field
>that he helped to establish, Woodward subsequently directed his
>efforts to other areas of organic chemistry. As a result, he missed
>out on a share of the 1973 Nobel Prize-a share that Woodward felt he
>Woodward's longtime friend and fellow Nobelist Sir Derek Barton
>summarized Woodward's feelings in this way :
>And when Geoff got a Nobel Prize for his work on ferrocene and its
>congeners, which he shared with E. O. Fischer, Bob Woodward said to
>me that it was rather strange, that he deserved to have that Nobel
>Prize. He didn't object to Geoff having one, too. But he certainly
>objected to the fact that he was not on that Prize. And they could
>have done that quite easily, because there was room for another
>Roald Hoffmann of Cornell University thinks that Woodward made a
>strategic error by not expanding his organometallic research efforts
>to include other transition metals and instead concentrating on the
>aromatic properties of ferrocene . Myron Rosenblum of Brandeis
>University feels that Woodward left the field because "perhaps he
>was more interested in the art and intellectual drama of organic
>In retrospect, it is hard- to second-guess Woodward's decision to
>concentrate on organic synthesis, structure elucidation, and theory.
>While Fischer and Wilkinson conducted their Nobel Prize-winning
>research in organometallic chemistry, Woodward received the 1965
>Nobel Prize in chemistry for his contributions to the "art of
>organic synthesis," developed the Woodward-Hoffmann rules for the
>conservation of orbital symmetry with Roald Hoffmann, and together
>with Albert Eschenmoser, led the team of chemists that completed the
>100-step total synthesis of vitamin B12.
>The Nobel Foundation's official record regarding the 1973 Nobel
>Prize in chemistry is closed to the public until 2023; however, a
>letter from then Nobel Chemistry Committee Chairman Holger Erdtman
>to Woodward's good friend and fellow Nobel laureate Lord Todd offers
>an unofficial explanation for the Nobel Committee's decision not to
>include Woodward in the 1973 Nobel Prize . This letter, dated
>December 13,1973, states:
>Thank you for your confidential letter of Nov. 30, from which I
>understand that Bob was distinctly upset--and perhaps not
>unreasonably--by the press reports of the award. However, I feel
>that the name Woodward has come a little out-of-the-way (if you
>understand that dictionary expression!). In the final declaration to
>the Academy it. is said that Woodward made a point contribution of
>value (of certain importance).
>Geoffrey Wilkinson and Robert Burns Woodward left a rich chemical
>legacy upon which future generations of chemists will continue to
>build. They also left a story, albeit an incomplete and irresolvable
>one, which speaks to the emotions of the people behind the
>scientific advances and discoveries.
>I want to thank Ed Atkinson, Derek Barton, Michael Becker, Mary
>Ellen Bowden, F. A. Cotton, Jack Dunitz, Dick Hill, Roald Hoffmann,
>Gail McMeekin, Myron Rosenblum, Leslie Orgel, Linda Simon, Leo
>Slater, Arnold Thackray, Lise Wilkinson, Crystal Woodward, Eudoxia
>Woodward, Marcia Yudkin, and members of the Harvard University
>Archives staff for their help and support during various phases of
>References and Notes
>1. Lindqvist, I. In Nobel Lectures in Chemistry 1971-1980,
>Frangsmyr, T., and Forsen, S., Eds.; World Scientific: Singapore,
>1993; pp 99-100.
>2. This is my personal observation based on interviews with some of
>Woodward's former co-workers.
>3. One unsubstantiated exception involves Woodward and a prominent
>4. HUG(FP) 68.10, Box 25, Nobel Prize II (folder 2). "By permission
>of the Harvard University Archives."
>5. Kealy, T. J.; Pauson, P. L. Nature 1951, 168,1039-1040.
>6. Miller, S: A.; Tebboth, J. A.; Tremaine, J. F. J Chem. Soc.
>(London) 1952, 632-635.
>7. Professor Myron Rosenblum, tape-recorded interview with Tom
>Zydowsky, Waltham, MA, August 28,1997.
>8. Wilkinson, G. J Organometal. Chem. 1975, 100, 273-278.
>9. Wilkinson, G.; Rosenblum, M.; Whiting, M. C.; Woodward, R. B. J.
>Am. Chem. Soc.1952, 74, 2123-2124.
>10. Geoffrey Wilkinson used the term "sandwich" in a 1952 paper
>(Wilkinson, G. J Am. Chem. Soc.1952, 74, 6148-49). Jack Dunitz and
>Leslie Orgel used the term "molecular sandwich" in their 1953 Nature
>paper (see Ref. 18, below) that they submitted three weeks after
>11. See footnote 41 in Pauson, P. L. Quart. Rev. 1955, 391-414.
>12. I want to thank Professor Roald Hoffmann for bringing this
>reference to my attention.
>13. HUG(FP) 68.10, Box 13, Correspondence-Personal, 1950-1953, "By
>permission of the Harvard University Archives."
>14. Eiland, P. F.; Pepinsky, R. J Am. Chem. Soc.1952, 74, 4971.
>15. Fischer, E. 0.; Pfab, W. Z. Naturforsch.1952, 76, 377-379.
>16: HUG(FP) 68.8, Box 13; Ferrocene (folder 1), "By permission of
>the Harvard University Archives."
>17. Dunitz, J. In Organic Chemistry: Its Language and Its State of
>the Art,- Kisakürek, M. V., Ed.; Verlag Helvetica Chimica Acta:
>Basel; VCH: Weinheim, New York, 1993; pp 9-23.
>18. Dunitz, J. D.; Orgel, L. E. Nature 1953, 171,121-124.
>19. Woodward, R. B.; Rosenblum, M.; Whiting, M. C. J Am. Chem.
>Soc.1952, 74, 3458-3459.
>20. Wilkinson, G. In Nobel Lectures in Chemistry 1971-1980;
>Frangsmyr, T., and Forsen, S., Eds.; World Scientific: Singapore,
>1993; pp 137-154.
>21. Seyferth, D.; Davison, A. Science 1973, 168, 699-701.
>22. HUG(FP) 68.10, Box 25, Nobel Prize II (folder 2), "By permission
>of the Harvard University Archives."
>23. Professor Derek Barton, tape-recorded interview with Tom
>Zydowsky, College Station, TX, November 22,1997.
>24. Professor Roald Hoffmann, tape-recorded interview with Tom
>Zydowsky, Ithaca, NY, May 14,1998.
>25. Professor Myron Rosenblum, personal communication to Tom
>Zydowsky, December 20,1998.
>26. HUG(FP) 68.10, Box 25, Nobel Prize II (folder 2), "By permission
>of the Harvard University Archives:"
>TOM ZYDOWSKY is an organic chemist and writer living in Worcester,
>Massachusetts. He received a Ph.D. (organic chemistry) at the
>University of Georgia with R.K. Hill.
>He is writing a series of articles on Woddward that will form a
>basis for a full biography. Anyone interested in contributing to the
>biography may contact Tom at 25 Harley Drive #6, Worcester, MA 01606
>or at <mailto:tmzinc$##$aol.com>tmzinc$##$aol.com.
>NESACS Phone: 800-872-2054 Contact the NESACS
><mailto:webmaster$##$nesacs.org>Webmaster with Comments or Questions.
>23 Cottage St. 508-653-6329 Natick, MA 01760
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