Synthesis and reactivity of dienyl–metal compounds. Part 30. Alkylation of thiolato bridges: a route to stable dialkyl sulphide bridged dinuclear molybdenum complexes. Crystal structure determination of [(η-C5H5)(CO)Mo(µ-SMe2)2Mo(PMe3)(η-C5H5)][BF4]2

Abstract

[{Mo(η-C₅H₅)(CO)(µ-SMe)}₂] is alkylated in two steps by [Me₃O]BF₄ to give the stable cations [{Mo(η-C₅H₅)(CO)}₂(µ-SMe)(µ-SMe₂)]⁺ and [{Mo(η-C₅H₅)(CO)(µ-SMe₂)}₂]²⁺. In the latter one carbonyl ligand can be replaced by PMe₃ or P(OMe)₃. The X-ray structure of [(η-C₅H₅)(CO)Mo(µ-SMe₂)₂Mo(PMe₃)(η-C₅H₅)][BF₄]₂ shows a slightly lengthened Mo–Mo double bond [2.693(1)Å] combined with a short Mo–S bond (ca. 2.34 Å).