TY - JOUR
T1 - Structure and reactivity of the anionic alkeneosmium cluster, [1,1,1,2,2,2,3,3,3,3-decacarbonyl-2-bromo-1-η2-trans-1,1, 1,4,4,4-hexafluorobut-2-ene-triangulo-triosmium]-
T2 - X-ray crystal structures of...
AU - Dawoodi, Zain
AU - Mays, Martin J.
AU - Raithby, Paul R.
AU - Henrick, Kim
AU - Clegg, William
AU - Weber, Gabriela
PY - 1983/6/21
Y1 - 1983/6/21
N2 - Title full: Structure and reactivity of the anionic alkeneosmium cluster, [1,1,1,2,2,2,3,3,3,3-decacarbonyl-2-bromo-1-η2-trans-1,1, 1,4,4,4-hexafluorobut-2-ene-triangulo-triosmium]-: X-ray crystal structures of [(Ph3P)2N][Os3(CO)10CF3 (H)CC(H)CF3Br], [(Ph3P)2N][Os3(CO)9CF 3(H)CC(H)CF3(μ-Br)], and [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)]. The η2-alkenebromoosmium cluster [Os3(CO)10CF3(H)CC(H)CF3Br] - (1) when refluxed in dichloromethane gives [Os3(CO)9CF3(H)CC(H)CF3(μ -Br)]- (2). On reaction with [Me3O]BF4 1 gives [HOs3(CO)10Br] and [Os3(CO)11trans-CF3(H)CC(H)CF 3] (3), whilst reaction with MeSO3F affords 3 and [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)] (4). To confirm structural conclusions based on 1H NMR, mass spectra and IR data, single crystal X-ray structures of the starting material and the two μ-Br products have been determined. Crystals of [Os3(CO)10CF3(H)CC(H)CF3Br][ PPN] (PPN = (Ph3P)2N) are monoclinic, space group P21/c, with a 15.521(4), b 8.863(3), c 37.497(11) Å, β 95.11(2)°, Z = 4, and final R = 0.047, Crystals of [Os3(CO)9CF3(H)CC(H)CF3(μ -Br)][PPN] are orthorhombic, space group Pbca, with a 15.725(5), b 20.194(8), c 32.295(12) Å, Z = 8, and final R = 0.068. Crystals of [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)] are monoclinic, space group C2/c, with a 27.670(3), b 9.225(2), c 16.799(3) Å, β 92.24(4)°, Z = 8 and final R = 0.082. In all three structures the alkene ligand is η2-bonded to one Os atom but the differing relative positions of the bromine atoms have a significant effect on the C-C alkene distance. The outcome of the reactions studied is interpreted in terms of the stabilising effect of the CF3 subtituents on the complexed alkene, both with respect to displacement and ligand modification.
AB - Title full: Structure and reactivity of the anionic alkeneosmium cluster, [1,1,1,2,2,2,3,3,3,3-decacarbonyl-2-bromo-1-η2-trans-1,1, 1,4,4,4-hexafluorobut-2-ene-triangulo-triosmium]-: X-ray crystal structures of [(Ph3P)2N][Os3(CO)10CF3 (H)CC(H)CF3Br], [(Ph3P)2N][Os3(CO)9CF 3(H)CC(H)CF3(μ-Br)], and [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)]. The η2-alkenebromoosmium cluster [Os3(CO)10CF3(H)CC(H)CF3Br] - (1) when refluxed in dichloromethane gives [Os3(CO)9CF3(H)CC(H)CF3(μ -Br)]- (2). On reaction with [Me3O]BF4 1 gives [HOs3(CO)10Br] and [Os3(CO)11trans-CF3(H)CC(H)CF 3] (3), whilst reaction with MeSO3F affords 3 and [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)] (4). To confirm structural conclusions based on 1H NMR, mass spectra and IR data, single crystal X-ray structures of the starting material and the two μ-Br products have been determined. Crystals of [Os3(CO)10CF3(H)CC(H)CF3Br][ PPN] (PPN = (Ph3P)2N) are monoclinic, space group P21/c, with a 15.521(4), b 8.863(3), c 37.497(11) Å, β 95.11(2)°, Z = 4, and final R = 0.047, Crystals of [Os3(CO)9CF3(H)CC(H)CF3(μ -Br)][PPN] are orthorhombic, space group Pbca, with a 15.725(5), b 20.194(8), c 32.295(12) Å, Z = 8, and final R = 0.068. Crystals of [HOs3(CO)9CF3(H)CC(H)CF3 (μ-Br)] are monoclinic, space group C2/c, with a 27.670(3), b 9.225(2), c 16.799(3) Å, β 92.24(4)°, Z = 8 and final R = 0.082. In all three structures the alkene ligand is η2-bonded to one Os atom but the differing relative positions of the bromine atoms have a significant effect on the C-C alkene distance. The outcome of the reactions studied is interpreted in terms of the stabilising effect of the CF3 subtituents on the complexed alkene, both with respect to displacement and ligand modification.
UR - http://www.scopus.com/inward/record.url?scp=0012771269&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)98806-5
DO - 10.1016/S0022-328X(00)98806-5
M3 - Article
AN - SCOPUS:0012771269
SN - 0022-328X
VL - 249
SP - 149
EP - 164
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -