Syntheses and crystal structures of new selenido- and selenolato-bridged copper clusters: [Cu38Se13(SePh)(12)(dppb)(6)] (1), [Cu(dppp)(2)][Cu25Se4(SePh)(18)(dppp)(2)] (2), [Cu36Se5(SePh)(26)(dppa)(4)] (3), [Cu58Se16(SePh)(24)(dppa)(6)] (4), and [Cu-3(SeMes)(3)(dppm)] (5)

The reactions of copper(I) chloride or copper(I) acetate with monodentate p hosphine ligands (PR3; R = organic group) and Se(SiMe3)(2) have already lea d to the formation of CuSe clusters with up to 146 copper and 73 selenium a toms. If the starting materials and the bidentate phosphine ligands (Ph2P-( CH2)(n)-PPh2, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph2P-C=C-PPh2: dppa) a nd silylated chalcogen derivates are changed (RSeSiMe3; R = Ph, Mes) a seri es of new CuSe clusters can be synthesized. From single crystal X-ray struc ture analysis one can characterise [Cu38Se13(SePh)(12)(dppb)(6)] (1), [Cu(d ppp)(2)] [Cu25Se4(SePh)(18)(dppp)(2)] (2), [Cu36Se5(SePh)(26)(dppa)(4)] (3) , [Cu58Se16(SePh)(24)(dppa)(6)] (4) and [Cu-3(SeMes)(3)(dppm)] (5). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.