Hydride and borohydride derivatives of (pentamethylcyclopentadienyl)(tertiary phosphine)ruthenium

Article abstract of DOI:10.1021/om00150a032

Reaction of NaBH₄ with (η⁵-C₅Me₅)RuCl₂(PR₃) (1) in ethanol results in the formation of trihydrides (η⁵-C⁵Me⁵)RuH₃(PR₃) (2, R = PMe₃, PEt₃, P(i-Pr)₃, PCy₃, PPh₂Me, PPh₃), the last of which is structurally characterized by a single-crystal X-ray diffraction study. (η⁵-C₅Me₅)RuH₃(PPh₃) crystallizes in the triclinic space group P1 with two molecules in a unit cell of dimensions a = 11.568 (2) A?, b = 13.012 (2) A?, c = 9.169 (1) A?, α = 91.12 (2)°, β = 89.72 (2)°, and γ = 116.60 (1)°. The molecule is shown to have pseudo C_s symmetry. The reaction of 1 with NaBH₄ in THF yields tetrahydroborate complexes (η⁵-C₅Me₅)Ru(PR₃)(BH ₄) (4, R = PMe₃, PEt₃, PCy₃, PPh₂Me, PPh₃), which are converted to the trihydrides 2 by treatment with ethanol. Irradiation of 2c and 2f with UV light in C₆D₆ causes the H/D exchange reaction among the hydrides, the coordinated phosphine, and the solvent.