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• W1996025561 endingPage "4516" @default.
• W1996025561 startingPage "4509" @default.
• W1996025561 abstract "The Rh(III) species Rh(PCy3)2H2Cl is an effective catalyst (2 mol %, 298 K) for the dehydrogenation of H3B·NMe2H (0.072 M in 1,2-F2C6H4 solvent) to ultimately afford the dimeric aminoborane [H2BNMe2]2. Mechanistic studies on the early stages in the consumption of H3B·NMe2H, using initial rate and H/D exchange experiments, indicate possible dehydrogenation mechanisms that invoke turnover-limiting N-H activation, which either precedes or follows B-H activation, to form H2B═NMe2, which then dimerizes to give [H2BNMe2]2. An additional detail is that the active catalyst Rh(PCy3)2H2Cl is in rapid equilibrium with an inactive dimeric species, [Rh(PCy3)H2Cl]2. The reaction of Rh(PCy3)2H2Cl with [Rh(PCy3)H2(H2)2][BAr(F)4] forms the halide-bridged adduct [Rh(PCy3)2H2(μ-Cl)H2(PCy3)2Rh][BAr(F)4] (Ar(F) = 3,5-(CF3)2C6H3), which has been crystallographically characterized. This dinuclear cation dissociates on addition of H3B·NMe2H to re-form Rh(PCy3)2H2Cl and generate [Rh(PCy3)2H2(η(2)-H3B·NMe2H)][BAr(F)4]. The fate of the catalyst at low catalyst loadings (0.5 mol %) is also addressed, with the formation of an inactive borohydride species, Rh(PCy3)2H2(η(2)-H2BH2), observed. On addition of H3B·NMe2H to Ir(PCy3)2H2Cl, the Ir congener Ir(PCy3)2H2(η(2)-H2BH2) is formed, with concomitant generation of the salt [H2B(NMe2H)2]Cl." @default.
• W1996025561 created "2016-06-24" @default.
• W1996025561 creator A5004567326 @default.
• W1996025561 creator A5008351342 @default.
• W1996025561 creator A5008796870 @default.
• W1996025561 creator A5031577471 @default.
• W1996025561 creator A5038608013 @default.
• W1996025561 date "2013-04-01" @default.
• W1996025561 modified "2023-09-26" @default.
• W1996025561 title "Dehydrocoupling of Dimethylamine Borane Catalyzed by Rh(PCy₃)₂H₂Cl" @default.
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