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

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

Fingerprint

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

Cite this

DuBois, D. L., Kvietok, F., & DuBois, M. R. (1993). A molecular orbital comparison of molybdenum-sulfur dimers with sulfide ligands bridged by CH2 and FeCp fragments. Inorganic Chemistry, 32(5), 561-564. https://doi.org/10.1021/ic00057a012

@article{416088a3ab504cf489c2f94fc9db5667,

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.",

author = "DuBois, {Daniel L} and F. Kvietok and DuBois, {M. Rakowski}",

year = "1993",

doi = "10.1021/ic00057a012",

language = "English",

volume = "32",

pages = "561--564",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - A molecular orbital comparison of molybdenum-sulfur dimers with sulfide ligands bridged by CH2 and FeCp fragments

AU - DuBois, Daniel L

AU - Kvietok, F.

AU - DuBois, M. Rakowski

PY - 1993

Y1 - 1993

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.

UR - http://www.scopus.com/inward/record.url?scp=5244329410&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=5244329410&partnerID=8YFLogxK

U2 - 10.1021/ic00057a012

DO - 10.1021/ic00057a012

M3 - Article

AN - SCOPUS:5244329410

VL - 32

SP - 561

EP - 564

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -

Access to Document

10.1021/ic00057a012