Systematic Approach for the Construction of Niobium and Tantalum Sulfide Clusters

Treatment of the imido complexes [MCl3(NR)­py2] (R = t Bu, 2,6-Me2C6H3; M = Nb 1, 3; Ta 2, 4) (Xyl = 2,6-Me2C6H3) with (Me3Si)2S in a 1:1 ratio afforded the new cube-type sulfide clusters [MCl­(NR)­py­(μ3-S)]4 (R = t Bu, 2,6-Me2C6H3; M = Nb 5, 7; Ta 6, 8) with loss of Me3SiCl. Reactions of 5 and 6 with cyclopentadienyllithium in 1:4 ratio resulted in the rupture of the coordinative M–S bonds and the replacement of a pyridine molecule and a chlorine atom by an η5-cyclopentadienyl group in each metal center, affording the compounds [M­(η5-C5H5)­(N t Bu)­(μ-S)]4 (M = Nb 9, Ta 10). These processes may develop through formation of the complexes [M4(η5-C5H5)2(μ-Cl)­(N t Bu)4py2(μ3-S)2­(μ-S)2]­(C5H5) (M = Nb 11, Ta 12), also obtained by reaction of 5 and 6 with cyclopentadienyllithium in 1:3 ratio. As further evidence, 11 and 12 led to complexes 9 and 10 by treatment with one more equivalent of the lithium reagent. The structural study of these metal sulfide clusters has been also performed by X-ray crystallography.