Ferrocene Story

ESSAY
Ferrocene: Ironclad History or Rashomon Tale?**

Pierre Laszlo and Roald Hoffmann*
A critical stance is essential to science. Proving other

people wrong is a favorite private and public satisfactionÐ ª...Mike Rosenblum came into my laboratory asking if I
there is nothing some scientists like better. But, excess zeal had got any ruthenium. I cant remember what I said, except
discounted, doubt serves as a powerful impulse to the that I think it was along the lines of let me tell you what you
advancement of knowledge. We document it here with the want it for. º
discovery of the structure of ferrocene, a story which also
plays up the virtue of the spoken word.[1] We base it on various Clearly, Wilkinson had already also seen the Kealy and
published (and most fragmentary, if not mutually inconsis- Pauson paper and had decided to study this problematic
tent!) accounts, supplemented with some very helpful corre- structure of ferrocene.[4]
spondence from colleagues. Wilkinson continues:
Two groups independently reported at the very end of 1951 ªHowever, the upshot was that Woodward and I had lunch at
preparation of a compound C10H10Fe from cyclopentadiene. the Harvard Faculty Club on Monday[5] and sorted things
Kealy and Pauson published their contribution in the out. The possibility that the C5H5 ring in the iron compound
December 15, 1951 edition of Nature, while Miller, Tebboth, could possibly undergo Friedel ± Crafts or other aromatic
and Tremaines account of their independent (and apparently reactions simply had not dawned on me, but other than the
earlier) preparation of the identical compound, with the same structure, this seemed to be Bobs main interest, whereas
ªtraditionalº formulation (what would today be called a di-s- mine was to go on to other transition metals.º
complex), appeared a little later in the Journal of the Chemical
Society.[2] One can only bemoan the fact that Woodward left no
Lets turn to the reception of those two papers in the account of the discovery, and apply all the reservations the
Chemistry Department at Harvard University. As soon as it science historian has painfully had to learn of the construction
arrived in the library, during the first couple of weeks in of history (yes, even by the very participants) after the fact.
January 1952, R. B. Woodward apparently saw the Kealy and Myron Rosenblum offers a some what different perspective
Pauson piece. And he had a hunch that the structure was on the directions taken by the protagonists:[3]
wrong. He set a graduate student, Myron Rosenblum,
ªWoodward certainly had an interest in extending the
preparing not only ferrocene, but also analogues from other
metallocene series vertically along the periodic table and
transition metals and cyclopentadiene. For this Rosenblum
possibly horizontally as well, since I set up four reactions
needed ruthenium trichloride. He went to Geoffrey Wilkin-
simultaneously on January 31st. These involved the reac-
son, who had recently taken up an Assistant professorship at
tions of NiCl2 , CoCl2, CrCl3 , and RuCl3 with cyclopenta-
Harvard, to ask for a sample of ruthenium. Wilkinson ªrather
dienylmagnesium bromide. From my research notebook I
brusquely wanted to knowº what Rosenblum needed it for.[3]
see that I had actually made two attempts to prepare
Wilkinson writes:[4]
anhydrous RuCl3 on January 16th, five days prior to my first
preparation of ferrocene itself. But in any event, Woodward
and Wilkinson had apparently reached a private agreement
which apparently left this initiative (extending the ferrocene
[*] Prof. R. Hoffmann family) to Geoff.º
Department of Chemistry, Cornell University
Baker Laboratory, Ithaca, NY 14853-1301 (USA) Woodwards contribution to the ferrocene story (and dare
Fax: ( 1) 607-255-5707 one identify this as the main contribution, too?) was the divina-
E-mail: rh34@cornell.edu
tion of the sandwich structure, and a beautiful piece of insight
P. Laszlo
Laboratoire de Chimie, Ecole Polytechnique
about its aromaticity. Of the latter Rosenblum writes: [3]
91128 Palaiseau CeÂdex (France)
Fax: ( 33) 169 333 010
ªOn a Thursday evening, March 13th (1952), as we were
E-mail: pierre.lazlo@ugl.ac.be taking our seats before that evenings seminar, we were
[**] Akira Kurosawas classic film ªRashomonº depicts a violent event (a chatting about some of the chemistry of this new substance,
rape and murder in a forest) as seen by four participants. In his when [RBW] suggested simply, almost matter-of-factly, that
autobiography (A. Kurosawa, Something Like an Autobiography, I might want to try a Friedel ± Crafts reaction on this new
Vintage Books ±Random House, New York, 1983, p. 183). Kurosawa
substance....I put off doing the reaction until Monday,
writes of the difficulty his co-workers had understanding the complex
plot. He told them: ªThis film is like a strange picture scroll that is March 17th...the product was a beautiful red crystalline
unrolled and displayed by the ego...you cant understand the script at material with an enormous carbonyl stretching absorption in
all, but that is because the human heart itself is impossible to the infrared. º
understand.º
Angew. Chem. Int. Ed. 2000, 39, No. 1 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0570-0833/00/3901-0123 $ 17.50+.50/0 123
ESSAY
The correct ferrocene structure and its aromaticity were most Also from the outset it was clear that this incredible
rapidly published in the form of a communication in Journal breakthrough, opening up a whole new field within organo-
of the American Chemical Society;[6] the coauthors were aside metallic chemistry, was worthy of recognition. It led to the
from Wilkinson and Woodward, Rosenblum and Mark C. award of the Nobel Prize to both Wilkinson and Fischer.
Whiting (a postdoctoral associate in the Woodward group, Woodward was inexplicably left out; he complained, of course
who joined the research effort). to no avail. Access to the deliberations of the Nobel
Meanwhile, during the spring of 1952, E. O. Fischer was Committee still decades in the future, Thomas Zydowsky
independently studying the structure of ferrocene in his has nevertheless uncovered the fascinating correspondence
laboratory at the Technische Hochschule in Munich (with W. that ensued, one that will also reveal Woodwards perspective
Pfab). Basing his conclusions on evidence from X-ray on the initial discovery. But for that story you will have to
crystallography, and on very reasonable bonding notions, he wait.[15]
also concluded that the molecule was best formulated as an
iron(ii) atom in-between two cyclopentadienide rings as We are grateful to many who have shared their memories and
ligands. Fischer and his co-workers immediately synthesized writings with us, most importantly Myron Rosenblum, Peter
the ferrocenium cation, and started exploring cognate mole- Pauson, Tom Zydowsky, Mark Whiting, Jack Dunitz, and
cules such as the corresponding cobaltocene.[7] F. Albert Cotton.
The structures proposed by Wilkinson, Woodward, Rose-
nblum, Whiting, Fischer, and Pfab were truly revolutionary.
Contemporary chemists were shocked; here is a recent [1] We expand here upon a segment from a recent paper aimed at
account by one of the greatest of structural chemists, J. D. sociologists, ªThe Say of Thingsº: R. Hoffmann, P. Laszlo, Soc. Res.
1998, 65, 653 ± 693.
Dunitz: [8] [2] T. J. Kealy, P. L. Pauson, Nature 1951, 168, 1039 ± 1040; S. A. Miller,
J. A. Tebboth, J. F. Tremaine, J. Chem. Soc. 1952, 632 ± 635. For a
ªOne afternoon, I opened the Library copy of JACS [in description of the chemistry and chronology of these two papers, see
Cambridge, England] and came across R. B. Woodwards G. B. Kauffman, J. Chem. Educ. 1983, 60, 185 ± 186.
proposal that the molecule consists of two parallel cyclo- [3] Letters from Professor Myron Rosenblum, Brandeis University, to
pentadienyl rings with the iron atom sandwiched between Roald Hoffmann of September 9, 1998, and March 29, 1999.
[4] G. Wilkinson, J. Organomet. Chem. 1975, 100, 273 ± 278; Wilkinson
them. I was skeptical. Nothing like this had ever been seen dates the visit by Rosenblum to Saturday, January 31st. However,
before. On my way out of the Library I met Leslie [Orgel] from the evidence in Rosenblums notebook, the visit predates
and asked if he had seen this astonishing proposal. He was as January 16, 1952. January 30th, 1952 was a Wednesday.
skeptical as I was. When we found that the compound was [5] The evidence of the Rosenblum notebooks would seem to indicate
January 19 and 21 for those dates.
relatively easy to prepare in crystalline form, I decided to
[6] G. Wilkinson, M. Rosenblum, M. C. Whiting, R. B. Woodward, J. Am.
determine its crystal structure and so demonstrate the Chem Soc. 1952, 74, 2125 ± 2126.
incorrectness [our emphasis] of the proposed molecular- [7] E. O. Fischer, W. Pfab, Z. Naturforsch. B 1952, 7, 377 ± 379.
structure. Within a few weeks, it became clear to us that [8] J. D. Dunitz, Origins Life and Evolution of the Biosphere 1997, 27,
Woodwards proposal was correct after all. There was no 421 ± 427. See also ªForty Years of Ferroceneº: J. D. Dunitz in Organic
Chemistry: Its Language and Its State of the Art (Ed.: M. V.
doubt about it.º Kisakurek), Verlag Helvetica Chimica Acta, Basel, 1993, pp. 9 ± 23.
[9] L. E. Orgel, J. D. Dunitz, Nature 1953, 171, 121 ± 122.
Leslie Orgel went on to devise a MO description of this [10] A third group independently determined the structure of ferrocene:
novel structure, which he published together with Dunitzs P. F. Eiland, R. Pepinsky, J. Am. Chem. Soc. 1952, 74, 4971.
structure determination. The title of their paper contained the [11] Peter Pauson, private communication, recalls that he had crystals of
ªsandwichº descriptor.[9±11] Which stuck.[12] ferrocene in the fall of 1951. He was trying to decide whether to ask
Jack Dunitz, or the senior organic crystallographer of the time, J.
Thus the ferrocene story unfolded: a conjectured structure Monteath Robertson (real or adopted Scotsmen all). Pauson decided
was intuitively doubted, refuted, and replaced with what we on Robertson. Who, according to Pauson, took the crystals to...Cor-
now know as the true structure. But the true structure was nell, where he asked Lynn Hoard if someone could look at them. The
deemed so unusual that it itself led to an attempt at refutation. crystals were assigned to a beginning graduate student, who failed to
solve the structure.
Which failed, and thereby became an outstanding piece of
[12] The felicitous coining of the name ªferroceneº is due to Mark Whiting
corroborative evidence. and occurs in the second Harvard paper, R. B. Woodward, M.
Our story is hardly complete! There is something to be Rosenblum, M. C. Whiting, J. Am. Chem. Soc. 1952, 74, 3458.
learned (will it be done before the traces vanish?) of the Apparently ªferrozeneº was an early favorite (e-mail from M. C.
complicated interactions that the experimentalists whose Whiting to Roald Hoffmann, May 4, 1999).
[13] Wilkinson, for instance recounts that William Moffitt, a great young
names we have mentioned above had with the theoreticians theoretician of the time, told him that the binding of benzene to a
around them.[13] And the sandwich structure was apparently transition metal was ªnot onº (ref. [4], footnote on p. 278).
suggested by William von E. Doering to Peter Pauson in [14] See footnote 41 of P. L. Pauson, Q. Rev. 1955, 391 ± 414.
September 1951, before the synthesis was published![14] [15] T. M. Zydowsky [tmzinc@aol.com], Chemical Intelligencer, in press.
124 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0570-0833/00/3901-0124 $ 17.50+.50/0 Angew. Chem. Int. Ed. 2000, 39, No. 1

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ESSAY

Ferrocene: Ironclad History or Rashomon Tale?**

A critical stance is essential to science. Proving other

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