Synthese und Strukturen neuer selenido‐ und selenolatoverbrückter Kupfercluster: [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) und [Cu3(SeMes)3(dppm)] (5)

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 Cu₃(SeMes)₃(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR₃; R = organic group) and Se(SiMe₃)₂ have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. 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) and silylated chalcogen derivates are changed (RSeSiMe₃; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise 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 Cu₃(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.