Syntheses and characterization of nickel(II) and ruthenium(II) complexes with the novel phosphine ligands 1-((diphenylphosphino)methyl)-1-phenyl-1-silacyclopent-3-ene and 1,1-bis ((diphenylphosphino)methyl)-1-silacyclopent-3-en. Crystal structure of

摘要

The reaction of the lithium salt of chlorodiphenylphosphine with 1-chloro-1-phenylsilacyclopent-3-ene (1) and 1, 1-dichlorosilacyclopent-3-ene (2) gave good yields of 1-((diphenylphosphino)methyl)-1-phenyl-1-silacyclopent-3-ene (L) (3) and 1,1-bis((diphenylphosphino)-methyl)-1-silacyclopent-3-ene (L') (4), Both molecules were obtained as white solids characterized by NMR. Red and red-violet diamagnetic square-planar complexes trans-NiCl2L2 and cis-NiCl2L' were obtained by reacting NiCl2. 6H(2)O with 3 and 4, respectively. Substitution of two PPh3 in CpRuCl(PPh3)(2) by 4 gave CpRuCl(L') (7) in good yield. Orange crystals of 7 contain monomeric pseudooctahedral ruthenium(II) centers surrounded by a Cl atom, a Cp ligand, and the two phosphorus atoms of the 1,1-bis((diphenylphosphino)methyl)-1-silacyclopent-3-ene ligand, The silacyclopentene ring adopts a puckered ground state configuration with a puckering angle of 10 degrees, 7 can be described as a spirannic compound with roughly perpendicular Ru-P(1)-C(10)-Si-C(20)-P(2) and Si-C(6)-C(7)-C(8)-C(9) rings. [References: 39]