摘要
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[MoW_2S_(10)]^(2-)晶体是第一次报道的Mo—W—S混合簇化合物。
Acidity of the media played an important role in forming chain Mo—S and W—S clusters. We found that (NH_4)_2MoS_4 and (NH_4)_2MoOS_3 were converted to dinuclear cluster (n-Bu_4N)_2(Mo_2OS_7) and trinuclear cluster [(n-Bu)_4N]_2(Mo_3O_2S_8) or (Ph_4P)_2(Mo_3S_9) in different acidic solutions. In CH_3CO_2H/CH_3OH system (NH_4)_2WS_4 was converted to tetranuclear cluster (n-Bu_4N)_2(W_4S_(12)) and trinuclear cluster (Me_(34)N)_2(W_3S_10). But when (NH_4)_2WOS_3 was used as starting material, trinuclear cluster (n-Bu_4N)_2. (W_3O_2S_8) was obtained. In dilute HCl aqueous solution, (NH_4)_2WS_4 or (NH_4)_2WOS_3 was converted to (n-Bu_4N)_2(W_3OS_8). Cluster (Ph_4P)_2 (MoW_2S_10) is the heteronuclear cluster which contain molybdenum, tungsten and sulfur reported for the first time. Here the regularity of the formation of chain cluster of (NH_4)_2MO_nS_(4-n), (M=Mo, W n=0, 1, 2) under acidic condition is suggested. In Chain Mo—S and W—S clusters, terminal sulfur atoms linked with the metal, especially in trinuclear clusters, were more reactive somehow. They could be removed readily either by tertiary phosphine or by cyanide to form terminal oxo-substitution products.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1990年第5期466-471,共6页
Acta Chimica Sinica
基金
国家自然科学基金
