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

Journal Article · Sun Feb 01 04:00:00 EST 1981 · Proc. Natl. Acad. Sci. U.S.A.; (United States)

DOI:https://doi.org/10.1073/pnas.78.2.668· OSTI ID:6507796

Davis, J H ^[1]; Beno, M A; Williams, J M; Zimmie, J A; Tachikawa, M; Muetterties, E L

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1. Argonne National Lab., IL

Molecular metal clusters with carbide carbon atoms of low coordination number have been prepared; they are the anionic (HFe/sub 4/C(CO)/sub 12//sup -/) and (Fe/sub 4/C(CO)/sub 12//sup 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/sub 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 A average). Protonation of the anionic carbide clusters reversibly yielded HFe/sub 4/(CH)(CO)/sub 12/, and methylation of the dianion gave (Fe/sub 4/(CC(O)CH/sub 3/)(CO)/sub 12//sup -/). Oxidation of (Fe/sub 4/C(CO)/sub 12//sup 2 -/) yielded the coordinately unsaturated Fe/sub 4/C(CO)/sub 12/ cluster, which was extremely reactive. Hydrogen addition to this iron cluster was rapid below 0/sup 0/C, and a C-H bond was formed in this transformation.

• OSTI ID: 6507796
• Journal Information: Proc. Natl. Acad. Sci. U.S.A.; (United States), Journal Name: Proc. Natl. Acad. Sci. U.S.A.; (United States) Vol. 78:2; ISSN PNASA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BOND LENGTHS
CRYSTAL STRUCTURE
DATA
DIMENSIONS
EXPERIMENTAL DATA
INFORMATION
IRON COMPOUNDS
LENGTH
MOLECULAR STRUCTURE
NUMERICAL DATA
TRANSITION ELEMENT COMPOUNDS