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Cluster chemistry

1988; Elsevier BV; Volume: 347; Issue: 1-2 Linguagem: Inglês

10.1016/0022-328x(88)80282-1

1872-8561

Michael I. Bruce, Michael J. Liddell, Omar bin Shawkataly, Caroline A. Hughes, Brian W. Skelton, Allan H. White,

Carbon dioxide utilization in catalysis

The molecular structures of Ru3(CO)9(L)3 (L = PMe2(CH2Ph), PMe2Ph, AsMe2Ph, PPh(OMe)2, P(OEt)3 and P(OCH2CF3)3) and Os3(CO)9(PPh3)3 have been determined by single-crystal X-ray diffraction methods. The tertiary phosphine, arsine or phosphite ligands occupy equatorial sites, one per metal atom, so arranged that each is as far from the other two as possible. The unit cell of the PPh(OMe)2 complex is unusual in containing four conformationally distinct molecules, two of which contain disordered Ru3 cores. Metalmetal and metalligand separations are similar to those found in Me3(CO)12 and mono- or disubstituted complexes, respectively. Considerable distortion towards D3 symmetry is found, with MMCO angles approaching those calculated for semi-bridging CO groups in the case of the P(OEt)3 complex. Crystal data: Ru3(CO)9(PMe2Ph)3, orthorhombic, P212121, a 21.343(2), b 14.752(4), c 12.170(2) Å, U 3832(1) Å3, Z = 4, N0 (number of ‘observed’ data with I > 3σ(I)) = 3601, R = 0.040, R′ = 0.048; Ru3(CO)9-(AsMe2Ph)3, triclinic, P1, a 19.113(4), b 15.375(4), c 13.756(3) Å, α 89.36(2), β 85.97(2), γ 77.61(2) °, U 3939(2) Å3, Z = 4, N0 = 8823, R = 0.046, R′ = 0.047; Ru3(CO)9{PMe2(CH2Ph)}3, trigonal, P3, a 12.766(10), c 15.583(9) Å, U 2202(2) Å3, Z = 2, N0 = 1966; R = 0.093, R′ = 0.117; Ru3(CO)9{PPh(OMe)2}3, triclinic, P1, a 23.23(1), b 20.87(1), c 20.73(1) Å, α 98.21(4), β 111.07(3), γ 111.95(4) °, U 8237(7) Å3, Z = 8, N0 = 16532, R = 0.041, R′ = 0.039; Ru3(CO)9{P(OEt)3}3, triclinic, P1, a 18.170(6), b 13.016(6), c 10.035(3) Å, α 68.83(3), β 80.42(3), γ 78.10(4) °, U 2154(1) Å3, Z = 2, N0 = 4318, R = 0.051, R′ = 0.061; Ru3(CO)9{P(OCH2CF3)3}3, triclinic, P1, a 21.036(2), b 13.146(1), c 9.376(2) Å, α 82.68(1), β 88.40(1), γ 85.59(1) °, U 2564(1) Å3, Z = 2, N0 = 3966, R = 0.066, R′ = 0.068; Os3(CO)9(PPh3)3, triclinic, P1, a 18.207(5), b 17.911(6), c 12.928(3) Å, α 94.13(2), β 98.98(2), γ 110.56(2) °, U 3862(2) Å3, Z = 2, N0 = 3216, R = 0.092, R′ = 0.084.