Synthesis and characterization of the [(CO)4MoS2MS2]2- and [(CO)4MoS2MS2Mo(CO)4]2- ions (M = Mo, W): species containing group VI (6) metals in widely separated formal oxidation states

Abstract

Dinuclear and trinuclear sulfide-bridged complexes of the types (Et/sub 4/N)/sub 2/(MS/sub 4/(Mo(CO)/sub 4/)) and (Et/sub 4/N)/sub 2/(MS/sub 4/(Mo(CO)/sub 4/)/sub 2/) were prepared by the reaction of one or two equivalents of Mo(CO)/sub 4/(C/sub 7/H/sub 8/) (C/sub 7/H/sub 8/ = norbornadiene) with (Et/sub 4/N)/sub 2/(MS/sub 4/) (M = Mo, W) in methyl alcohol. Elemental analyses were consistent with the proposed formulae. Infrared spectra of all four compounds contain strong bands in the carbonyl region and low-energy bands characteristic of terminal and bridging M-S vibrations in linear, polynuclear, and sulfido-bridged species. Electrochemical experimental results support the hypothesis that the di- and trinuclear species contain both M(IV) (M = Mo, W) and Mo(0) oxidation states in the same complex. 33 references, 2 tables.