Cyclopentadienyl-ruthenium and -osmium chemistry. Part 11. Reactions and structures of [RuCl(PPh3)2(η-C5H5)] and its trimethyl-phosphine analogue
Abstract
The crystal structure of the title compound has been determined by single-crystal X-ray diffraction at 295 K and refined by least squares to a residual of 0.036 for 7 290 ‘observed’ reflections. Crystals are triclinic, space group P, with a= 14.493(8), b= 11.315(4), c= 11.745(4)Å, α= 69.99(3), β= 84.67(4), γ= 62.27(3)°, and Z= 2. The ruthenium environment is pseudo-tetrahedral, Ru–Cl 2.453(2), Ru–P 2.337(1), 2.335(1), <Ru–C(n)> 2.207Å. The phenyl ring environments are highly crowded and the nature of the steric interactions between them is examined. The structure of the trimethylphosphine analogue [RuCl(PMe3)2(C5H5)] has also been determined, 1 805 ‘observed’ reflections being refined to a residual of 0.059. Crystals are orthorhombic, space group Pbca, with a= 29.251(8), b= 14.703(4), c= 14.649(7)Å, and Z= 16. The two ruthenium environments are similar to that of the triphenylphosphine analogue. The Ru–Cl distances are 2.451 (6), 2.440(5), and Ru–P 2.273(5)–2.280(6)Å. The value of <Ru–C(n)> is 2.20 Å. The syntheses and properties of [RuCl(PMe3)2(η-C5H5)] and of the cationic derivatives [RuL(PMe3)2(η-C5H5)]+(L = MeCN, CO, CNBut, or PMe3) are also described.