Hieber

First hydrido complex of a transition metal prepared by W. Hieber and F. Leutert. 

In 1931, Hieber and Leutert reported Fe(CO)4(H)2 not only as the first iron hydride complex but also as the first transition-metal hydride complex (FeH2 was reported in 1929 from FeCl2 and PhMgBr under a hydrogen atmosphere. However, it exists only in a gas phase) [2, 3]. The complex synthesized from Fe(CO)5 and OH (Scheme 1) is isolable only at low temperature and decomposes at room temperature into Fe(CO)5, Fe(CO)3, and H2. 

The low-valent ferrate [Fe(CO)3(NO)] 76 or Hieber anion was discovered some 50 years ago by Hieber and Beutner [43, 44] in order to extend the Hieber base reaction [45,46], in which iron pentacarbonyl 78 reacts with alkaline bases to form the [Fe(CO)4] anion [47, 48]. Compared to its homoleptic analogue, the Hieber anion is more stable because the electron-withdrawing character of the nitrosyl ligand stabilizes the negative charge at the iron atom. 

With Roustan et al. using the sodium salt of the Hieber anion 76-Na, the procedure was improved by Xu and Zhou in 1987 when they introduced the corresponding shelf-stable tetrabutylammonium salt 76-[Bu4N] which is available from Fe(CO)5 78, NaN02 and Bu4NBr (Scheme 17) [61,62]. As well as discovered by Roustan they obtained the substitution products with an ipso-preference (Scheme 16) albeit in a significantly lower yield. In order to maintain the catalytic activity of the product, the reactions were performed under CO-gas atmosphere. 

After these encouraging results, it is surprising that no further investigations have been performed on this reaction, which might be attributed to problems regarding catalyst stability, reproducibility, or the use of a problematic CO gas atmosphere. The comeback of the Hieber anion dates back to 2006 when our group... 

Apart from this mechanistic hypothesis, another scenario, with a ferrate complex as intermediate, may be possible. In 1928, Hieber discovered that Fe(CO)5 78 underwent a disproportionation in the presence of ethylenediamine 122 [97-101]. Depending on the reaction temperature, different ferrate complexes were formed that incorporated a [Fe(en)3] cation (en = ethylenediamine) and mono-, di- or trinuclear ferrate anions (Scheme 32) [102-107]. As the reaction discussed above is also performed with amines at high temperatures, these ferrates may well be involved in the catalytic cycle of the carbonylation discussed above. 

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