Synthesis, structures and properties of bis(carbodiimido) complexes of Ni(II), Pd(II) and Pt(II)

摘要: Bis(azido)–Group 10 metal complexes (M(N3)2L2) reacted with two equivalents of isocyanides (CNR) to give the corresponding bis(carbodiimido) complexes, M(NCN–R)2L2 {[Pd(NCN–2,6-Me2C6H3)2L2]: L = PMe3 (1), PEt3 (2), PMe2Ph (3); [Pd(NCN–2,6-Et2C6H3)2L2]: (4); [Ni(NCN–2,6-Me2C6H3)2L2]: (5), (6); [Pt(NCN–2,6-Me2C6H3)2L2]: (7), (8)} in relatively high yields. Reaction schemes have been proposed on basis isolated intermediates such as Ni[CN4(R)](NCN–R)(PMe3)2 (R 2,6-Me2C6H3) (9), trans-Pt[CN4(R)]2(PMe3)2 (10), and Pt[CN4(R)](NCN–R)L2 (L (11) or PEt3, (12)). Molecular structures 1, 2, 4, 6, 8, 11 determined by X-ray diffraction, demonstrating that nitrogen carbodiimido (NCN) group is directly bonded center. The chelating phosphine analogues M(N3)2(L–L) {M Pd Ni; L–L depe (1,2-bis(diethylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), dppe (1,2-bis(diphenylphosphino)ethane)} also M(NCN–R)2(L–L) Pd: (13), (14); M Ni, (15)} Treating Pd(NCN–2,6-Me2C6H3)2(PMe3)2 (1) benzoyl chloride (PhCOCl), phenyl chloroformate (PhOCOCl), 2-thiophenecarbonyl (C4H3SCOCl) gave organic cyanamides, PhCON(CN)-2,6-Me2C6H3, PhO(CO)N(CN)-2,6-Me2C6H3, C4H3SCON(CN)-2,6-Me2C6H3, respectively.