Abstract
X-Ray crystal structures of six complexes M 3(CO) 11(L) (M = Ru, L = PPh(OMe) 2, P(OCH 2CF 3) 3, P(OCH 2) 3CEt and AsPh 3; M = Os, L = PPh 3 and PPh(OMe) 2) have been determined. Consideration of these results, together with other published data, allowed several conclusions to be drawn concerning the effect of substituting one CO group in M 3(CO) 12 (M = Ru, Os) by a P, or As-donor ligand. The most important are that L occupies an equatorial site, the MM separation cis to L increases with increasing cone angle of L, while the CO eq ligand cis to L on the same metal atom is more tighly bound. Distortions of the M 3L 12 molecule from D 3 h to D 3 geometry appear to be related to the σ-donor properties of L. The reactions between Ru 3(CO) 12 and P(OCH 2CF 3) 3, and between Os 3(CO) 12 and PPh 3 or PPh(OMe) 2, to give M 3(CO) 12− n (L) n( n = 1–3), are described. Crystal data: Ru 3(CO) 11{PPh(OMe) 2}, monoclinic, P 2/ c, a 9.647(3), b 20.529(7), c 14.692(5) Å, β 119.93(2)°, U 2522(1) Å 3, Z = 4, N 0 (observed data, with > 3σ( I)) = 5829, R = 0.035, R′ = 0.037; Ru 3(CO) 11{P(OCH 2CF 3) 3}, triclinic, P 1 , a 12.920(1), b 11.530(2), c 10.189(1) Å, a 85.93(1), β 86.57(1), γ 70.66(1)°, U 1427(1) Å 3, Z = 2, N o = 4061, R = 0.038, R′ = 0.054; Ru 3(CO) 11{P(OCH 2) 3CEt}, monoclinic P2 1/ c, a 13.57(1), b 14.779(1), c 12.362(3) Å, β 98.34(4)°, U 2453(1) Å 3, Z = 4, N o = 5950, R = 0.039, R′ = 0.054; Ru 3(CO) 11(AsPh 3), monoclinic, C2/ c, a 22.496(6), b 16.348(4), c 17.345(5) Å, β 103.65(2)°, U 6198(3) Å 3, Z = 8, N o = 6071, R = 0.032, R′ = 0.028; Os 3(CO) 11(PPh 3, monoclinic, C2/ c, a 22.196(5), b 16.265(3), c 17.370(5) Å, β 103.86(2)°, U 6088(3) Å 3 Z = 8, N o = 4125, R = 0.031, R′ = 0.033; Os 3(CO) 3(CO) 11{PPh(OMe) 2}, monoclinic, P2 1/ c, a 10.817(3), b 14.993(4), c 16.174(3) Å, β 101.87(2)°, U 2567(1) Å, Z = 4, N o = 5506, R = 0.047, R′ = 0.057.
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