Synthesen und Kristallstrukturen neuer chalkogenido‐verbrückter Niob‐Kupfer‐Cluster

Syntheses and Crystal Structures of Novel Chalcogenido‐bridged Niobium Copper Clusters In the presence of tertiary phosphines, the reaction of NbCl5 and Copper(I) salts with Se(SiMe3)2 (E = S, Se) affords the new chalcogenido‐bridged niobium‐copper cluster compounds $^{1}_{\infty}\rm [NbCu_{2}Se_{4}(P^{i}Pr_{2}Me)_{3}]$ (1) and [NbCu4Se4Cl (PPh3)4] (2). Using E(R)SiMe3 (E = S, Se, R = Ph, nPr) instead of the bisilylated selenium species leads to the compounds [NbCu2(SPh)6(PMe3)2] (3), [NbCu2(SPh)6(PnPr3)2] (4), [NbCu2(SePh)6(PMe3)2] (5), [NbCu2(SePh)6(PnPr3)2] (6), [NbCu2(SePh)6(PiPr3)2] (7), [NbCu2(SePh)6(PtBu3)2] (8), [NbCu2(SePh)6(PiPr2Me)2] (9), [NbCu2(SePh)6(PPhEt2)2] (10), [Nb2Cu2(SnPr)8(PnPr3)2Cl2] (11) and [Nb2Cu6(SnPr)12(PiPr3)2Cl4]·2 CH3CN (12·2 CH3CN). By reacting CuI salts and NbCl5 with the monosilylated selenides Se(tBu)SiMe3 and Se(iPr)SiMe3 which have a weak Se–C bond the products [Nb2Cu6Se6(PiPr3)6Cl4] (13), [Nb2Cu4Se2(SeiPr)6(PnPr3)4Cl2] (14) and [Nb2Cu6Se2(SeiPr)10(PEt2Me)2Cl2]·DME (15) are formed which contain selenide as well as alkylselenolate ligands. The molecular structures of all of these new compounds were determined by single crystal X‐ray diffraction measurements.