497066-20-3Relevant academic research and scientific papers
Synthesis, structures and properties of bis(carbodiimido) complexes of Ni(II), Pd(II) and Pt(II)
Kim, Yong-Joo,Joo, Young-Seon,Han, Jin-Taek,Han, Seok Won,Lee, Soon W.
, p. 3611 - 3618 (2007/10/03)
Bis(azido)-Group 10 metal complexes (M(N3)2L2) reacted with two equivalents of isocyanides (CNR) to give the corresponding bis(carbodiimido) complexes, M(N=C=N-R)2L2 {[Pd(N=C=N-2,6-Me2C6H3)2L 2]: L = PMe3 (1), PEt3 (2), PMe2Ph(3); [Pd(N=C=N-2,6-Et2C6H3)2L 2]: L = PMe3 (4); [Ni(N=C=N-2,6-Me2C6H3)2L 2]: L = PMe3 (5), PEt3 (6); [Pt(N=C=(N-2,6-Me2C6H3)2L 2]: L = PMe3 (7), PEt3 (8)} in relatively high yields. Reaction schemes have been proposed on the basis of isolated intermediates such as Ni[CN4(R)](N=C=N-R)(PMe3)2 (R=(2,6-Me2C6H3) (9),(trans)(-Pt[CN4(R)]2-(PMe3)2 (10), and Pt[CN4(R)](N=C=N-R)L2 (L = PMe3 (11) or PEt3, (12). Molecular structures of 1, 2, 4, 6, 8, and 11 have been determined by X-ray diffraction, demonstrating that the nitrogen of the carbodiimido (N=C=N) group is directly bonded to the metal center. The chelating phosphine analogues M(N3)2(L-L) {M = Pd or Ni; L-L = depe (1,2-bis(diethylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), or dppe (1,2-bis(diphenylphosphino)-ethane)} reacted with isocyanides to also give the corresponding bis(carbodiimido) complexes, M(N=C=N-R)2-(L-L) {M = Pd: L-L = depe (13), dppp (14); M = Ni, L-L = dppe (15)} in high yields. Treating Pd(N=C=N-2,6-Me2C6H3)2(PMe 3)2 (1) with two equivalents of benzoyl chloride (PhCOCl), phenyl chloroformate (PhOCOCl), and (2-thiophenecarbonyl chloride (C4H3SCOCl) gave organic cyanamides, PhCON(CN)-2,6-Me2C6H3, PhO(CO)N(CN)-2,6-Me2C6H3, and C4H3SCON(CN)-2,6-Me2C6H 3, respectively.
