Discovery of Cuprous thiocyanate

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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(EBu)] (IIIa: E? = E = S; IIIb: 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 eta2 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 mu4 bridging selenide ligands forming an octahedra. The compounds 1-15 are listed below: (NEt4)?1[Cu2NbSe 2S2(dppe)2] ¡¤ 2 DMF (1), [Cu3NbS4(PPh3)4] (2), [Au3NbSe4(PPh3)4] ¡¤ Et2O (3), [Cu4NbS4Cl(PCy3)4] (4), [Cu4NbS4Cl(PBu3)4] ¡¤ 0,5 DMF (5), [Cu4NbSe4(NCS)(PBu3)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[Cu3Nb2S 4(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. WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”