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Issue 47, 2009
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Butterfly and rhombus structures for binuclear cobalt carbonyl sulfur and phosphinidene complexes of the type Co2(CO)6E2 (E = S, PX)

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Abstract

Theoretical studies on Co2(CO)6(PX)2 derivatives (X = H, Cl, OH, OMe, NH2, NMe2) predict the lowest energy structures to be butterfly structures containing five two-electron two-center bonds in the central Co2P2 unit. Among these butterfly structures the energy increases as the unique bond forming the “body” of the butterfly changes from Co–Co to Co–P and then P–P. Higher energy rhombus structures are also found for Co2(CO)6(PX)2 with only Co–P bonds in the Co2P2 framework without any Co–Co or P–P bonds. In addition, for Co2(CO)6(POR)2 (R = H, Me) still higher energy “diphosphine” structures are also found containing only three rather than four Co–P bonds, one P–P bond, and no Co⋯Co bond. For the isoelectronic Co2(CO)6S2 a rhombus structure is competitive in energy with the butterfly structures with five structures lying within ∼4 kcal/mol thereby predicting a fluxional system. A tetrahedrane structure was not found for Co2(CO)6S2 in contrast to the tetrahedrane structure known experimentally for the related Fe2(CO)6S2 with one less electron per metal atom.

Graphical abstract: Butterfly and rhombus structures for binuclear cobalt carbonyl sulfur and phosphinidene complexes of the type Co2(CO)6E2 (E = S, PX)

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Publication details

The article was received on 02 Jul 2009, accepted on 01 Oct 2009 and first published on 09 Nov 2009


Article type: Paper
DOI: 10.1039/B913117E
Dalton Trans., 2009, 10474-10480

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    Butterfly and rhombus structures for binuclear cobalt carbonyl sulfur and phosphinidene complexes of the type Co2(CO)6E2 (E = S, PX)

    G. Li, Q. Li, I. Silaghi-Dumitrescu, R. B. King and H. F. Schaefer III, Dalton Trans., 2009, 10474
    DOI: 10.1039/B913117E

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