100514-77-0Relevant academic research and scientific papers
Chemistry and catalytic properties of ruthenium and osmium complexes. 2. Synthesis and characterization of new mononuclear and dinuclear complexes with hydride, carboxylate, and phosphine ligands. X-ray crystal and molecular structures of OsBr(OCOMe)(CO) (PPh3)2, RuCl(OCOMe)(CO) (PPh3)2, and [PPh3Me]+[Ru ...
Sánchez-Delgado, Roberto A.,Thewalt, Ulf,Valencia, Norma,Andriollo, Antida,Márquez-Silva, Rosa-Linda,Puga, José,Sch?llhorn, Helmut,Klein, Heinz-Peter,Fontal, Bernardo
, p. 1097 - 1106 (2008/10/08)
Full title: Chemistry and catalytic properties of ruthenium and osmium complexes. 2. Synthesis and characterization of new mononuclear and dinuclear complexes with hydride, carboxylate, and phosphine ligands. X-ray crystal and molecular structures of OsBr(OCOMe)(CO) (PPh3)2, RuCl(OCOMe)(CO) (PPh3)2, and [PPh3Me]+[Ru2Cl2(μ-Cl) 3(CO)2(PPh3)2]-. The synthesis and characterization of a number of new compounds are reported. RuHBr(CO)(PPh3)3 is prepared by reaction of RuH(OCOMe)(CO)(PPh3)2, with excess HBr, followed by treatment with H2, NEt3, and PPh3. Halo-carboxylate complexes MX(OCOR)(CO)(PPh3)2 (M = Ru, X = Cl, R = CH2Cl; M = Ru, X = Br, R = CH3; M = Os, X = Cl, Br, R = CH3) are obtained from the hydrides MHX(CO)(PPh3)3 by reaction with the appropriate acid, while hydrido-carboxylate complexes RuH(OCOR)(CO)(PPh3)2 (R = CMe3, C6H11, CH2Cl, CF2Cl) result from the reaction of RuH2(CO)(PPh3)3 with carboxylic acids. Also, a novel reaction of RuHCl(CO)(PPh3)3 with CF3CO2H, CH2ClCO2H, and HBF4, leading to three new dinuclear compounds, is described. All complexes have been characterized by analytical and spectroscopic (IR and 1H and 31P NMR) methods. In addition, structural details for two mononuclear complexes and one dinuclear complex are presented. OsBr(OCOMe)(CO)(PPh3)2 crystallizes in the monoclinic space group P21/n with a = 9.760 (2) A?, b = 20.379 (4) A?, c = 17.462 (3) A?, β = 96.45 (2)°, and Z = 4. The structure converged to a conventional R factor of 0.048 for 3923 observations and 195 variables. The five ligands about the osmium adopt a highly distorted octahedral arrangement with the phosphines occupying mutually cis positions and the carboxylate bound in an asymmetric bidentate manner. RuCl(OCOMe)(CO)(PPh3)2 crystallizes in the monoclinic space group K21/c with a = 17.776 (5) A?, b = 9.696 (2) A?, c = 20.862 (6) A?, β = 106.35 (3)°, and Z = 4. The structure has been refined to a conventional R factor of 0.111 for 6769 observations and 213 parameters. The CO and Cl ligands exhibit positional disorder. The Ru atom shows a distorted octahedral environment with the phosphines occupying mutually trans positions cis to the carboxylate, which is bound in a bidentate symmetric manner. [PPh3Me]+[Ru2Cl2(μ-Cl) 3(CO)2-(PPh3)2]- CH2Cl2 crystallizes in the monoclinic space group P21/n with a = 19.966 (10) A?, b = 14.383 (6) A?, c = 20.064 (6) A?, and β = 93.36 (4)°. The structure has been refined to R = 0.079 for 6581 independent diffractometer data and 349 parameters. The Ru?Ru distance is 3.257 (1) A?. The anion has noncrystallographic m symmetry (if one neglects the differences of PPh3 conformations). The μ-Cl-Ru bond distances for the μ-Cl atoms trans to the PPh3 groups are significantly longer than those for the μ-Cl atoms trans to the Cl ligands (2.488 (2) and 2.510 (2) A? compared with 2.405 (2) and 2.402 (2) A?).
