Pilar Resano Barrio, Miguel A. Esteruelas, E. Oñate
Feb 13, 2004
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0
Influential Citations
67
Citations
Journal
Organometallics
Abstract
The hexahydride complex OsH6(PiPr3)2 (1) activates the C−Hα bond of aldehydes. In toluene under reflux, the reactions with benzaldehyde, cyclohexanecarboxaldehyde, and isobutyraldehyde lead to products resulting from two C−Hα activation−decarbonylation tandem processes. The reaction with benzaldehyde gives the hydride-phenyl-cis-dicarbonyl derivative OsHPh(CO)2(PiPr3)2 (2) and benzene, while cyclohexanecarboxaldehyde and isobutyraldehyde yield the cis-dihydride-cis-dicarbonyl compound OsH2(CO)2(PiPr3)2 (3) and the corresponding alkane. In the presence of water 1 reacts with benzaldehyde to give 2. However, cyclohexanecarboxaldehyde and isobutyraldehyde afford the carboxylate complexes OsH3(κ2-O2CR)(PiPr3)2 (R = Cy (4), (CH3)2CH (5)), which can also be obtained by reaction of 1 and the corresponding carboxylic acid. Similarly, the treatment of 1 with benzoic acid gives OsH3 (κ2-O2CPh)(PiPr3)2 (6). The structure of 5 in the solid state has been determined by X-ray diffraction analysis. The coordination geom...