链状钼硫, 钨硫原子簇合物的合成和成簇规律的研究

本文报道了不同酸性条件下合成的一系列链状钼硫、钨硫簇化合物, 发现硫代钼(钨)酸铵的成簇与酸的强度、浓度、H^+/M(M=Mo、W)比、溶剂、反应气氛密切相关。测定了四个新簇合物的晶体结构, 其中MoW2S10]^2^-晶体是第一次报道的Mo-W-S混合簇化合物。

Studies on synthesis and regularity of cluster formation of Mo-S, W-S chain compounds

(NH4)2MoS4 and (NH4)2MoOS3 were converted to (Bu4N)2(Mo2OS7) and (Bu)4N]2(Mo3O2S8) or (Ph4P)2(Mo3S9) in different acidic solns. In HOAc/MeOH system (NH4)2WS4 was converted to (Bu4N)2(W4S12) and (Me4N)2(W3S10). When (NH4)2WOS3 was used as starting material, (Bu4N)2(W3O2Ss) was obtained. In dilute HCl aqueous solution, (NH4)2WS4 or (NH4)2WOS3 was converted to (Bu4N)2(W3OS8). (Ph4P)2(MoW2S10) is a heteronuclear cluster which contains Mo, W, and S. The regularity of the formation of chain cluster of (NH4)2MOnS4-n (M = Mo, W; n = O-2) under acidic condition is suggested. In chain Mo-S and W-S clusters, terminal S atoms linked with the metal, especially in trinuclear clusters, were more reactive. They could be removed readily either by tertiary phosphine or by cyanide to form terminal oxo-substitution products.