Assembly of molecular squares and helical chain polymers of Mo(W)/Cu/S clusters using thiolato ligands as linkers

摘要

Reactions between thiomolybdate or thiotungstate [Et4N](2)[MS4] (M = Mo W) and CuSBu' led to the formation of two novel Mo(W)/Cu/S Clusters [Et4N](4)[{MS4Cu2(mu-SBu')}(4)] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 2 is the first example of a molecular square containing CuS2WS2Cu building blocks. The reactions of [Et4N](2)[MS4] with CuCl followed by the addition of K2SSS (SSS = 1,3,4-thiadiazole-2,5-dithiolate) yielded novel polymers {[Et4N](2)[MS4Cu2(SSS)]}(n) (3, M = Mo; 4, M = W). Crystal structure determination shows that the CuS2WS2Cu building blocks in the anion of 4 are bridged by SSS2- ligands to produce a helical chain running down the crystallographic b axis. (c) 2005 Elsevier Ltd. All rights reserved.