Hydrido-nitrosyl clusters [M3(CO)10H(NO)](M = Ru or Os) and the molecular and crystal structure of [Ru3(CO)7H(NO){P(OMe)3}3]

Abstract

The hydrido-nitrosyl cluster [Ru₃(CO)₁₀H(NO)] has been prepared in high yield from the reaction of Na[Ru₃(CO)₁₁H] with [NO][PF₆]. The corresponding osmium complex, [Os₃(CO)₁₀H(NO)], has been prepared in lower yield from Na[Os₃(CO)₁₁H]. The complex [Ru₃(CO)₁₀H(NO)] reacts with P(OMe)₃ to produce the trisubstituted complex [Ru₃(CO)₇H(NO){P(OMe)₃}₃], which crystallises in the monoclinic space group P2₁/c with cell dimensions a= 14.666(4), b= 12.743(4), c= 18.384(7)Å, β= 112.57(3)°, and Z= 4. The structure has been solved by a combination of multisolution sigma-2 sign-expansion and Fourier techniques, and refined by full-matrix least squares to R 0.052 for 4 547 unique observed intensities. The three ruthenium atoms define an isosceles triangle, the shortest edge of which is symmetrically bridged by both a nitrosyl and a hydrido-ligand. The complex [Ru₃(CO)₁₀H(NO)] reacts with PPh₃ to give the three related complexes [Ru₃(CO)_10–nH(NO)(PPh₃)_n](n= 1–3).