Papers by Dang Minh Phat B2007574
Journal of the American Chemical Society, 1973
more easily (+0.32 V compared to +0.55 V) and rapidly oxidized than the corresponding aquo comple... more more easily (+0.32 V compared to +0.55 V) and rapidly oxidized than the corresponding aquo complex. The band which causes the blue color is at shorter wavelength for the ammine (585 nm compared to 605 nm). Incomplete studies of a series of blue ruthenium chloride complexes suggest that there is a good correlation between the basicity of the terminal ligands and the wavelength of the maximum of this band. The nature of this transition is not known, but this correlation suggests that it may involve the d electrons which are of T symmetry in octahedral complexes. In the dimeric complexes these electrons are very likely to be involved in metal-metal bonding. With both the ammine and aquo complexes, oxidation beyond the ruthenium(II1) state apparently re-6429 sults in disruption of the coordination sphere. The most striking difference in the two complexes occurs in the reaction leading to their formation. When HC1 is added to R U (H Z O)~~+ no hydrogen is evolved. However, after a few hours a ruthenium mirror is deposited on the walls of the reaction vessel. Apparently this reaction proceeds by a disproportionation, while hydrogen ion is the oxidizing agent in producing RuLCll-(NH 3)6 2+ from hexaammineruthenium(I1). Acknowledgments. The authors express their thanks to the U. S. Atomic Energy Commission for financial support which made this study possible. We also thank Dr. T. J. Meyer for suggesting that the blue chloroammines may be related to the aquo complexes which we were studying. Asymmetric Catalytic Reduction with Transition Metal Complexes. I. A Catalytic System of Rhodium(I) with (-)-2,3-O-Isopropylidene-2,3-dihydroxy-1.4-bis (diphenylphosphino) butane, a New Chiral Diphosphine
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Papers by Dang Minh Phat B2007574