[CU24S12(PMEIPR(2))(12)], [CU28S14(PTBU(2)ME)(12)], [CU50S25(PTBU(2)ME)(16)], [CU70SE35(PTBU(2)ME)(21)], [CU31SE15(SESIME(3))(PTBU(2)ME)(12)] AND [CU48SE24(PME(2)PH)(20)] - NEW SULFUR-BRIDGED AND SELENIUM-BRIDGED COPPER CLUSTERS

Reaction of copper(I) acetate with bis(trimethylsilyl)chalcogenides E- (SiMe(3))(2) (E = S, Se) in the presence of tertiary phosphines in org anic solvents leads to the formation of chalcogen-bridged copper clust ers in crystalline form. In recent investigations, the following struc tures were isolated and characterised by X-ray crystallography: [Cu24S 12(PMeiPr(2))(12)] (1), [Cu28S14(PtBu(2)Me)(12)] (2), [Cu50S25(PtBu(2) Me)(16)] (3), [Cu70Se35(PtBu(2)Me)(21)] (4), [Cu31Se15(SeSiMe(3))(PtBu (2)Me)(12)] (5) and [Cu48Se24(PMe(2)Ph)(20)] (6). The cluster cores of 1-6 have new structures or new structural characteristics and go some way towards providing an insight into the mechanisms of cluster forma tion reactions. With the help of the aforementioned compounds a number of structure principles that govern sulfur- and selenium-bridged copp er clusters can be formulated.