Reactions of polynuclear thio- and oxothiocomplexes of molybdenum and tungsten with Co(II), Ni(II), Cu(I) and Au(I) chlorides

Abstract

Reactions of some polynuclear thio- and oxothiocomplexes of molybdenum and tungsten with Co(II), Ni(II), Cu(I) and Au(I) chlorides have been studied. Interaction of (Et 4N) 2W 3S 9 and (Et 4N) 2W 4S 12 with Ph 3PMCl (M=Cu, Au) is accompanied by elimination of WS 4 2− fragments giving rise to the heterometallic thiocomplexes (Ph 3P) 3Cu 2WS 4 and (Ph 3P) 2Au 2WS 4. The latter complex has been obtained in quantitative yield in the reaction of mononuclear WS 4 2− with Ph 3PAuCl or [(Ph 3PAu) 3O]BF 4. The binuclear oxothiocomplex (Bu 4N) 2Mo 2S 7O interacts with Co, Ni and Cu chlorides to form amorphous thiocomplexes (Bu 4N)Cu(Mo 2S 7O) and (Bu 4N) 2M(Mo 2S 7O) 2 (M=Co, Ni). According to IR data the (Mo 2S 7O) 2− fragment remains intact in these complexes. Polynuclear thiocomplexes can also act as a source of sulfur with respect to weak Lewis acids. Reaction of the heterometallic thiocomplex (Ph 3P) 2Au 2WS 4 with a source of electrophilic particles Ph 3PAu + results in complete desulfuration of the thiocomplex and formation of [(Ph 3PAu) 3S] BF 4 in high yield.