Ferrocene - History

History

Ferrocene was first prepared unintentionally. In 1951, Pauson and Kealy at Duquesne University reported the reaction of cyclopentadienyl magnesium bromide and ferric chloride with the goal of oxidatively coupling the diene to prepare fulvalene. Instead, they obtained a light orange powder of "remarkable stability.". A second group at British Oxygen also unknowingly discovered ferrocene. Miller, Tebboth and Tremaine were trying to synthesise amines from hydrocarbons such as cyclopentadiene and ammonia in a modification of the Haber process. They published this result in 1952 although the actual work was done three years earlier The stability of the new organoiron compound was accorded to the aromatic character of the negative charged cyclopentadienyls, but they were not the ones to recognize the η5 (pentahapto) sandwich structure.

Robert Burns Woodward and Geoffrey Wilkinson deduced the structure based on its reactivity. Independently Ernst Otto Fischer also came to the conclusion of the sandwich structure and started to synthesize other metallocenes such as nickelocene and cobaltocene.

The structure of ferrocene was confirmed by NMR spectroscopy and X-ray crystallography. Its distinctive "sandwich" structure led to an explosion of interest in compounds of d-block metals with hydrocarbons, and invigorated the development of the flourishing study of organometallic chemistry. In 1973 Fischer of the Technische Universität München and Wilkinson of Imperial College London shared a Nobel Prize for their work on metallocenes and other aspects of organometallic chemistry.