| Abstract: | Chalcogenoniobates as Reagents for the Synthesis of New Heterobimetallic Niobium Coinage Metal Chalcogenide Clusters In the presence of phosphine chalcogenoniobates such as Li3[NbS4] · 4 CH3CN ( I ), (NEt4)4[Nb6S17] · 3 CH3CN ( II ) and (NEt4)2[NbE′3(EtBu)] ( III a : E′ = E = S; III b : E = Se, E′ = S; III c : E = E′ = Se) respectively react with copper and gold salts to give a number of new heterobimetallic niobium copper(gold) chalcogenide clusters. These clusters show metal chalcogenide units already known from the complex chemistry of the tetrachalcogenometalates [ME4]n– (M = V, n = 3, E = S; M = Mo, W, n = 2, E = S, Se). The compounds 1 – 8 owe a central tetrahedral [NbE4] structural unit, which coordinates η2 from two to five coinage metal atoms, employing the chalcogenide atoms of the [NbE4] edges. The compounds 9 – 11 have a [M′2Nb2E4] (M′ = Cu, Au) heterocubane unit in common, involving a metal metal bond between the niobium atoms, while the compounds 12 and 13 show a complete and 14 an incomplete [M′3NbE3X] heterocubane structure (X = Cl, Br). 15 consists of a Cu6Nb2 cube with the six planes capped by μ4 bridging selenide ligands forming an octahedra. The compounds 1 – 15 are listed below: (NEt4) [Cu2NbSe2S2(dppe)2] · 2 DMF ( 1 ), [Cu3NbS4(PPh3)4] ( 2 ), [Au3NbSe4(PPh3)4] · Et2O ( 3 ), [Cu4NbS4Cl(PCy3)4] ( 4 ), [Cu4NbS4Cl(PtBu3)4] · 0,5 DMF ( 5 ), [Cu4NbSe4(NCS)(PtBu3)4] · DMF ( 6 ), [Cu4NbS4(NCS)(dppm)4] · Et2O ( 7 ), [Cu5NbSe4Cl2‐ (dppm)4] · 3 DMF ( 8 ), [Cu2Nb2S4Cl2(PMe3)6] · DMF ( 9 ), [Au2Nb2Se4Cl2(PMe3)6] · DMF ( 10 ), (NEt4)2[Cu3Nb2S4(NCS)5(dppm)2(dmf)] · 4 DMF ( 11 ), [Cu3NbS3Br(PPh3)3(dmf)3]Br · [CuBr(PPh3)3] · PPh3 · OPPh3 · 3 DMF ( 12 ), [Cu3NbS3Cl2(PPh3)3(dmf)2] · 1.5 DMF ( 13 ), (NEt4)[Cu3NbSe3Cl3(dmf)3] ( 14 ), [Cu6Nb2Se6O2(PMe3)6] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis. |
