- Dehalogenation of hexachlorocyclohexanes and simultaneous chlorination of triethylsilane catalyzed by rhodium and ruthenium complexes
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Complexes RhCl(PPh3)3 and RhH2Cl(P iPr3)2 catalyze the dehalogenation of γ-hexachloro-cyclohexane to benzene and the simultaneous chlorination of HSiEt3 to ClSiEt3. In
- Esteruelas, Miguel A.,Herrero, Juana,Olivan, Montserrat
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- Using NMR and ESI-MS to probe the mechanism of silane dehydrocoupling catalyzed by wilkinson's catalyst
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The reaction of Wilkinson's catalyst Rh(PPh3)3Cl (1) with 1-2 equiv. of di-n-hexylsilane gives rise to a complex mixture of products, which has been analyzed by 31P{1H} NMR and shown to include the hydrido complex Rh(PPh3)3H (3). Continuous sampling of the 1:1 reaction mixture by ESI-MS provided time-dependent speciation that tracks the formation of 3 at the expense of the initial silane oxidative addition product [Rh(PPh3)2(Cl)(H){Si(nHex) 2H}] (2), the subsequent 1st order disappearance of 3, and the formation of other, minor side-products. Our results provide insight into established activity of 1 for catalytic dehydrocoupling of di-n-hexylsilane, and implicate complex 3 as the active species in this catalysis. The combination of 31P NMR and ESI-MS provides detailed insight into the dynamics of the activation of a secondary silaneby Rh(PPh3)3Cl, with strong evidence pointing to the role of Rh(PPh3)3H as the active catalyst for silane dehydrocoupling and to the deleterious effect of trace water in this system. Copyright
- Jackson, Sarah M.,Chisholm, Danielle M.,McIndoe, J. Scott,Rosenberg, Lisa
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p. 327 - 330
(2011/05/07)
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- Phosphinorhodium-catalyzed dehalogenation of chlorinated and fluorinated ethylenes: Distinct mechanisms with triethylsilane and dihydrogen
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Catalytic dehalogenation of chlorinated and fluorinated ethylenes by (PR3)3RhCl complexes is described. The C-Cl and C-F bonds are activated by the catalyst in the presence of triethylsilane (Et 3SiH) or dihydrogen (H
- Peterson, Alicia A.,Thoreson, Kristen A.,McNeill, Kristopher
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p. 5982 - 5991
(2010/02/16)
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