화학공학소재연구정보센터
Inorganic Chemistry, Vol.55, No.8, 3815-3821, 2016
Systematic Approach for the Construction of Niobium and Tantalum Sulfide Clusters
Treatment of the imido complexes [MCl3(NR)py(2)] (R =Bu-t, 2,6-Me2C6H3; M = Nb 1, 3; Ta 2, 4) (Xyl = 2,6-Me2C6H3) with (Me3Si)(2)S in a 1:1 ratio afforded the new cube-type sulfide clusters [MC1(NR)py(mu(3)-S)](4) (R = Bu-t, 2,6-Me2C6H3; M= Nb 5, 7; Ta 6, 8) with loss of Me3SiCI. 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 eta(5)-cydopentadienyl group in each metal center, affording the compounds [M(eta(5)-C5H5)((NBu)-Bu-t)(mu-S)](4) (M= Nb 9, Ta 10). These processes May develop through formation of the complexes [M-4(eta(5)-C5H5)(2)(mu-Cl)((NBu)-Bu-t)(4)py(2)(mu(3)-S)(2)(mu-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 arid 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 drystallOgraphy.