Cluster chemistry - LV. Stereochemistry of group 15 ligand-substituted derivatives of M"3(CO)"1"2 ( M = Ru, Os) A. X-Ray structures of six complexes M"3(CO)"1"1(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)

X-Ray crystal structures of six complexes M"3(CO)"1"1(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 publishe...
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X-Ray crystal structures of six complexes M"3(CO)"1"1(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)"1"2 (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"e"q ligand cis to L on the same metal atom is more tighly bound. Distortions of the M"3L"1"2 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)"1"2 and P(OCH"2CF"3)"3, and between Os"3(CO)"1"2 and PPh"3 or PPh(OMe)"2, to give M"3(CO)"1"2"-"n(L)"n(n = 1-3), are described. Crystal data: Ru"3(CO)"1"1{PPh(OMe)"2}, monoclinic, P"2/c, a 9.647(3), b 20.529(7), c 14.692(5) Å, β 119.93(2)^o, U 2522(1) Å^3, Z = 4, N"0 (observed data, with > 3σ(I)) = 5829, R = 0.035, R' = 0.037; Ru"3(CO)"1"1{P(OCH"2CF"3)"3}, triclinic, P1, 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)^o, U 1427(1) Å^3, Z = 2, N"o = 4061, R = 0.038, R' = 0.054; Ru"3(CO)"1"1{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)^o, U 2453(1) Å^3, Z = 4, N"o = 5950, R = 0.039, R' = 0.054; Ru"3(CO)"1"1(AsPh"3), monoclinic, C2/c, a 22.496(6), b 16.348(4), c 17.345(5) Å, β 103.65(2)^o, U 6198(3) Å^3, Z = 8, N"o = 6071, R = 0.032, R' = 0.028; Os"3(CO)"1"1(PPh"3, monoclinic, C2/c, a 22.196(5), b 16.265(3), c 17.370(5) Å, β 103.86(2)^o, U 6088(3) Å^3 Z = 8, N"o = 4125, R = 0.031, R' = 0.033; Os"3(CO)"3(CO)"1"1{PPh(OMe)"2}, monoclinic, P2"1/c, a 10.817(3), b 14.993(4), c 16.174(3) Å, β 101.87(2)^o, U 2567(1) Å, Z = 4, N"o = 5506, R = 0.047, R' = 0.057. Ausführliche Beschreibung