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.
ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry