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Journal of Organometallic Chemistry 637639 (2001) 1617Recollections of the arrival of ferroceneMark C. Whiting13 Canowie Road, Bristol BS6 7HP, UK(Mark Whiting ca. 1952)My interest in transition-metal organometallic chemistrybegan at Imperial College London in 1946 when Iwas asked by my supervisor, E.R.H. Jones, to work onthe Reppe carboxylation of acetylenes with nickel carbonyl1. Some experiments were also carried out withiron pentacarbonyl. By the summer of 1951, I hadobtained a lectureship, a tenured post, at the Universityof Manchester, but was preparing for a transatlanticvoyage in order to work as a postdoctoral fellow withR.B. Woodwardalready a name to conjure with.In July or August 1951 I received, as a Fellow of theChemical Society, my monthly copy of J. Chem. Soc.with an enclosure entitled Papers Received; at thattime JCS sent out each month a list of the titles andauthors of papers sent in. One of these was Dicyclopentadieneiron,by S.A. Miller, J.A. Tebboth, andJ.F. Tremaine 2. Evidently a compound Fe(C5H5)2existed, surely analogous in a sense to Fe(CO)5.I arrived at Harvard in September 1951 and workedat first on a variant of the Woodward steroid synthesis.After returning from a snowy Christmas with friends ofmy sister in Grand Rapids, Michigan, I found an airletter from my Manchester colleague Kathleen Farrercontaining an accurate precis of Peter Pausons descriptionof dicyclopentadienyliron, made from ferric chlorideand cyclopentadienyl magnesium bromide, and0022-328X/01/$ - see front matter 2001 Published by Elsevier Science B.V.PII: S0022-328X(01)01129-9M.C. Whiting / Journal of Organometallic Chemistry 637639 (2001) 1617 17evidently the compound I already knew of. When Naturereached Harvard later in the month, after the usualsea crossing, Bob Woodward at once appreciated theimportance of this substance (as I had not), and itbecame a major topic of conversation within the group.We soon predicted dibenzenechromium, dicyclobutadienylnickel,mixed cycloarenecarbonyls, etc., and firstMike Rosenblum and then I (to my delight) wereallowed to switch work to this area. Meanwhile, welearned that, along the corridor, Geoffrey Wilkinsonhad also become interested in it.When I made my first batch of the new compound, Iran its infrared spectrum in carbon tetrachloride solutionand saw that (at Baird prism-monochromator resolution)the C_H stretching band was a sharp singlet,actually sharper than benzene, which indicates that allthe C_H bonds were identical, as we had expected.Mike had run the spectrum in chloroform, as wasnormal practice in the Woodward group, and the C_Habsorption of the solvent had obscured the region. Ialso satisfied myself that the conversion of the orangepetrol-soluble compound to a blue water-soluble materialwas an oxidationthe view originally held by theother three workers but which had fallen into disfavour.This led to the three yellow solutions experiment,a neat trick: solutions were prepared of the newcompound and p-benzoquinone in ether and of picricacid in methanol. Mixing any two had little effect, butmixing all three produced a beautiful dark green precipitateof what we called ferricinium picrate. It was thisthat led me to suggest amending the name ferrozene,which we had begun to use, to ferrocene.By this time, Mike Rosenblum had effected the firstaromatic substitution; using carbon disulphide as solvent,acetyl chloride and aluminium chloride (a heterogeneoussystem) converted ferrocene into diacetylferrocene.I repeated the experiment with methylenechloride as solvent, giving a homogeneous system, andeasily separated the product into mono-acetylferroceneand a diketone fraction which itself was separated withgreat difficulty into Mikes compound, the main component,and another isomer. By now we had recognisedan infrared band at about 10 _m as characteristic ofunsubstituted cyclopentadienyl rings (C_H out of planebending). It was present in the mono-acetyl compoundand the new diacetyl compound, but it was absent fromthe main isomer. Obviously, the first acetyl group deactivatesthe ring in which it is present, which confirmsthe analogy with benzenoid aromatic substitution.A good deal of time was spent exploring the chemistryof ferrocene. Geoffrey Wilkinson, in particular,worked on the generalisation of this chemistry to othermetals, especially making cobalticinium salts. But whenI returned to Manchester in October 1952, there weremany other things I wanted to do and I was happy toleave the field in the hands of the WoodwardWilkinsonRosenblum and Pauson groups. However, I didre-enter it briefly at Oxford, where Barry Nichols and Iobserved the formation of the arenechromium tricarbonylsa potentially enormous group of compounds.Meanwhile, developments have fully vindicated BobWoodwards belief that ferrocene was a most importantmilestone.References1 E.R.H. Jones, T.Y. Shen, M.C. Whiting, J. Chem. Soc. 48 (1951)763, 766.2 S.A. Miller, J.A. Tebboth, J.F. Tremaine, J. Chem. Soc. (1952)623. 金属有机化学学报637639 (2001) 1617 二茂铁发现过程的回忆 Mark C. Whiting 13 Canowie Road, Bristol BS6 7HP, UK (Mark Whiting ca. 1952)我对过渡金属有机化合物的研究兴趣是从1946年在英国伦敦大学帝国理工学院开始的，当时我的指导老师（E.R.H. Jones）要求我从事乙炔和羰基镍之间的炔醛羧化反应。有些实验是在五羰铁的作用下完成。1951年的夏天，我获得了曼彻斯特大学的一个终身职位-做一名讲师，但是我仍然在为去大西洋彼岸做准备，为了能够以博士后的身份成为当时赫赫有名的罗伯特伯恩斯伍德沃德教授的同事。1951年7、8月份，作为一名化学学会的同事，我收到了一份附件标记有“文件已收到”来自于化学学会会刊的我的月刊。在那个时候化学学会会刊每月会将作者们寄来的文件的主题罗列成单寄出给所有成员。其中有一个就是“2环戊2烯铁化物” 由S.A. Miller, J.A. Tebboth和J.F. Tremaine发表的。显然，Fe(C5H5)2这种化合物是存在的，某种意义上来说和Fe(CO)5是类似的。我在1951年的9月到达哈佛大学，最开始从事于伍德沃德类固醇合成的多样性研究。一个下雪的圣诞节，我和我妹妹的一个朋友从Grand Rapids, Michigan,回来后，我发现一封从Manchester的一位同事Kathleen Farrer寄来的航空信，里面包含了对Peter Pauson关于2环戊2烯铁化合物描述的准确摘要。这种化合物是由氯化铁和环戊二烯基溴化镁生成。显然，这种化合物我已经知晓了。当Nature在这个月稍后到达哈佛大学的时候，Bob Woodward立刻肯定了这种化合物的重要性（但是我没有），并且这种化合物成为会议上小组内部的主要话题。我们很快地预言了二苯铬、dicyclobutadienylnicke、mixed cycloarenecarbonyls等等的存在。首先是Mike Rosenblum，其次是我被允许转换研究工作到这个领域。之后我们知道，在研究中，Geoffrey Wilkinson也已经对此有了兴趣。当我把我的第一批新化合物制造出来时，我做了它在四氯化碳中的红外光谱图，然后发现（用Baird棱镜单色仪分辨率）其中的CH伸缩振动是单谱线，事实上峰比笨的还要尖锐，这个说明了所有的CH键都是完全相同的，与我们的预期一致。Mike做了该化合物在氯仿当中的光谱，这是在Woodward小组中很常见的操作，然后发现溶剂的吸收掩盖了这个光谱区域。我对于这个从橘黄色油溶性的化合物转化成蓝色水溶性材料的反应是一个氧化反应也感到非常的满意。这个观点最初是由其他三位如今持反对意见的科学家提出来的。这个延伸出了“三黄溶剂”实验，一个圆滑的欺骗，溶剂已经做好了对新化合物的准备，对苯醌在乙醚中和苦味酸在甲醇中。任意混合其中的2中没有多大的效应，但是把三种混合起来就会产生一种漂亮的深绿色的沉淀，我们将这种沉淀成为二茂铁的苦味酸盐。正是基于此我才建议将它的名称由最初的“ferrozene”改为现在的“ferrocene”（二茂铁）。在这期间，Mik