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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-ene. Crystal Structure of CpRuCl[(PPh2CH2)2(SiC4H6)]
journal contribution
posted on 1998-06-05, 00:00 authored by Pascal Dufour, Valérie Capdevielle, Michèle Dartiguenave, Yves Dartiguenave, Francine Bélanger-Gariépy, André L. BeauchampThe 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
NiCl2·6H2O 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°. 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.