POLYMERS OF MS_4~(2-) (M = Mo, W) WITH Cu(I) AND Ag(I) : SYNTHESIS AND CHARACTERIZATION OF Me_4NCuMS_4 AND Me_4NAgMS_4 AND THEIR POLYMERIC CHAIN BREAKING REACTIONS WITH M'CN (M' = Cu, Ag) TO FORM CLUSTER COMPLEXES

摘要

Thiomolybdate (Ⅵ) and thiotungstate (Ⅵ) anions, MS_4~(2-), react with Cu(I)halides in 1:1 molar ratio at the boiling point of MeOH to give insoluble red-brown and orange-yellow solids of polymers Me_4NCuMoS_4 1 and Me_4NCuWS_4 2, respectively. Similarly, with Ag(I)halides they form Mo(W)-Ag polymers Me_4NAgMoS_4 3 and Me_4NAgWS_4 4, respectively. Undergoing polymeric chain breaking reactions with metal (I) cyanides, M'CN (M' = Cu, Ag), Me_4NCuMS_4 form reported soluble cluster complexes, Me_4N_2MS_4 (CuCN)_2 (M = Mo, W). The same clusters are prepared from the reactions of Me_4NAgMS_4 with CuCN. Me_4NAgMS_4 form known clusters Me_4N_2MS_4(AgCN with AgCN. The complexes have been characterized on the basis of elemental analysis, infrared, DTA and X-ray diffraction studies.