Structure and chemistry of a metal cluster with a four-coordinate carbide carbon atom

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Abstract
Molecular metal clusters with carbide carbon atoms of low coordination number have been prepared; they are the anionic [HFe 4 C(CO) 12 - ] and [Fe 4 C(CO) 12 2- ] clusters. An x-ray crystallographic analysis of a tetraaminozinc salt of the latter has established a butterfly array of iron atoms with the carbide carbon atom centered above the wings of the Fe 4 core. Each iron atom was bonded to three peripheral carbonyl ligands. The distances from the carbide carbon to iron were relatively short, particularly those to the apical iron atoms (1.80 Å average). Protonation of the anionic carbide clusters reversibly yielded HFe 4 (CH)(CO) 12 , and methylation of the dianion gave {Fe 4 [CC(O)CH 3 ](CO) 12 - }. Oxidation of [Fe 4 C(CO) 12 2- ] yielded the coordinately unsaturated Fe 4 C(CO) 12 cluster, which was extremely reactive. Hydrogen addition to this iron cluster was rapid below 0°C, and a C—H bond was formed in this transformation.

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