R. McCrindle, G. Ferguson, G. Arsenault
Jun 26, 1990
Citations
0
Influential Citations
5
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Treatment of bis(chloromethyl)(1,5-cyclooctadiene)platinum(II) (3) with tricyclohexylphosphine gave a product (4) which underwent anion exchange with ammonium hexafluorophosphate to give di-μ-chlorobis(2-tricyclohexylphosphonioethyl)bis(tricyclohexylphosphine)diplatinum(II) bis(hexafluorophosphate) (5) the structure of which was established by X-ray crystallography. 31P NMR indicates that the dication of 5 exists as a cis-trans mixture in solution and that in chloroform 4 has the structure cis-dichloro(2-tricyclohexylphosphonioethyl)(tricyclohexylphosphine)platinum(II). In more polar media the latter is in equilibrium with the same cis-trans dicationic pair. Crystals of 5 are triclinic, space group P 1 , with two molecules in a unit cell of dimensions a 14.917(2), b 14.950(3), c 10.476(2) A, α 96.20(2), β 106.43(2), γ 103.45(1)°. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations; R is 0.033 for 3825 observed reflections. In the solid state 5 exists as a centrosymmetric chlorine-bridged dimer, with square-planar platinum and PtP 2.229(2), PtCl 2.402(2) (trans to P), 2.450(2) (trans to CH2), PtCH2 2.052(8) A.