Crystal and Molecular Structure of Co6S8(PBu n3)6 and Synergism in the Cluster Core M6E8P6(E=S, Se, Te)

Abstract

Abstract: Hexanuclear cobalt-sulfur cluster complex Co₆S₈(PBu₃ⁿ)₆ is a new member of a series of cage like homonuclear clusters with skeleton [M₆E₈P₆]ⁿ, in which M=Cr, Mo, W, Fe, Co; E=S, Se, Te; n=-1, 0, +1, +2, +3. The Co₆ octahedron and the S₈ cubane of the title complex are intercalated to form the cluster core, with the Patoms terminally ligated to Co. The synthetic process and the crystal structure analysis show that the formation process can be viewed as the construction of three mononuclear species Co(PBu₃ⁿ)₂S to form a metastable trinuclear "synthon" Co₃(μ₂ S)₃(μ₃ S)(PBu₃ⁿ)₃, two of which then combine to form the final stable cluster Co₆S₈(PBu₃ⁿ)₆. Synergism within a molecule having skeleton M₆E₈P₆ was discussed from the following viewpoints: ease of cluster formation; high stability towards redox reaction; delocalization of valence electrons; electrons of the reduced states enter the anti-bonding orbitals; and the idea of metal-based valence electrons.

Key words: Cobalt-phosphine-sulfur cluster complexes, Hexanuclear clusters, Synergism effect, Crystal structure

CLC Number:

O641

TrendMD:

KANG Bei-Sheng, CHEN Zhong-Ning, SU Cheng-Yong, ZHENG Kang-Cheng, LIU Han-Qin, ZHOU Zhong-Yuan. Crystal and Molecular Structure of Co₆S₈(PBu n₃)₆ and Synergism in the Cluster Core M₆E₈P₆(E=S, Se, Te)[J]. Chem. J. Chinese Universities, 1998, 19(5): 760.

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Crystal and Molecular Structure of Co₆S₈(PBu n₃)₆ and Synergism in the Cluster Core M₆E₈P₆(E=S, Se, Te)

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