A molecular orbital comparison of molybdenum-sulfur dimers with sulfide ligands bridged by CH2 and FeCp fragments

Daniel L DuBois; F. Kvietok; M. Rakowski DuBois

doi:10.1021/ic00057a012

A molecular orbital comparison of molybdenum-sulfur dimers with sulfide ligands bridged by CH2 and FeCp fragments

Daniel L DuBois, F. Kvietok, M. Rakowski DuBois

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

An extensive reactivity with hydrogen and unsaturated molecules has been characterized for the μ-sulfide ligands in (CpMo)₂(μ-S) ₂S₂CH₂ (2). However, the bridging disulfide ligand in the heteronuclear cluster [(CpMo)₂(μS ₂)(μ-S₂FeCp)]⁺ (3) was not reactive toward hydrogen or olefins. Extended Huckel molecular orbital calculations have been carried out for 2 and for the hypothetical Fe-Mo cluster with bridging sulfides rather than a disulfide ligand [(CpMo)₂(μ-S)₂(S ₂FeCp)]⁺ (3'). The electronic structures of complexes 2 and 3' are analyzed in terms of the Cp₂Mo₂S₄ and methylene and the FeCp⁺ fragment orbitais, respectively. This approach leads to a qualitative understanding of the reasons for the structural and reactivity differences between 2 and 3.

Original language	English
Pages (from-to)	561-564
Number of pages	4
Journal	Inorganic Chemistry
Volume	32
Issue number	5
DOIs	https://doi.org/10.1021/ic00057a012
Publication status	Published - 1993

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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title = "A molecular orbital comparison of molybdenum-sulfur dimers with sulfide ligands bridged by CH2 and FeCp fragments",

abstract = "An extensive reactivity with hydrogen and unsaturated molecules has been characterized for the μ-sulfide ligands in (CpMo)2(μ-S) 2S2CH2 (2). However, the bridging disulfide ligand in the heteronuclear cluster [(CpMo)2(μS 2)(μ-S2FeCp)]+ (3) was not reactive toward hydrogen or olefins. Extended Huckel molecular orbital calculations have been carried out for 2 and for the hypothetical Fe-Mo cluster with bridging sulfides rather than a disulfide ligand [(CpMo)2(μ-S)2(S 2FeCp)]+ (3'). The electronic structures of complexes 2 and 3' are analyzed in terms of the Cp2Mo2S4 and methylene and the FeCp+ fragment orbitais, respectively. This approach leads to a qualitative understanding of the reasons for the structural and reactivity differences between 2 and 3.",

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AU - Kvietok, F.

AU - DuBois, M. Rakowski

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N2 - An extensive reactivity with hydrogen and unsaturated molecules has been characterized for the μ-sulfide ligands in (CpMo)2(μ-S) 2S2CH2 (2). However, the bridging disulfide ligand in the heteronuclear cluster [(CpMo)2(μS 2)(μ-S2FeCp)]+ (3) was not reactive toward hydrogen or olefins. Extended Huckel molecular orbital calculations have been carried out for 2 and for the hypothetical Fe-Mo cluster with bridging sulfides rather than a disulfide ligand [(CpMo)2(μ-S)2(S 2FeCp)]+ (3'). The electronic structures of complexes 2 and 3' are analyzed in terms of the Cp2Mo2S4 and methylene and the FeCp+ fragment orbitais, respectively. This approach leads to a qualitative understanding of the reasons for the structural and reactivity differences between 2 and 3.

AB - An extensive reactivity with hydrogen and unsaturated molecules has been characterized for the μ-sulfide ligands in (CpMo)2(μ-S) 2S2CH2 (2). However, the bridging disulfide ligand in the heteronuclear cluster [(CpMo)2(μS 2)(μ-S2FeCp)]+ (3) was not reactive toward hydrogen or olefins. Extended Huckel molecular orbital calculations have been carried out for 2 and for the hypothetical Fe-Mo cluster with bridging sulfides rather than a disulfide ligand [(CpMo)2(μ-S)2(S 2FeCp)]+ (3'). The electronic structures of complexes 2 and 3' are analyzed in terms of the Cp2Mo2S4 and methylene and the FeCp+ fragment orbitais, respectively. This approach leads to a qualitative understanding of the reasons for the structural and reactivity differences between 2 and 3.

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