[Rh(PCy3)2H2(η2-H3BNMe2H)][B(C6H3(CF3)2)4] | 1358755-13-1

• 英文名称: [Rh(PCy3)2H2(η2-H3BNMe2H)][B(C6H3(CF3)2)4]
• CAS: 1358755-13-1
• 化学式: C₃₂H₁₂BF₂₄*C₃₈H₇₈BNP₂Rh
• 分子量: 1587.93
• InChiKey: VZSOFHJQUZJUFY-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [Rh(PCy3)2(η2-H3BNMe2BH2Me2H)][B(C6H3(CF3)2)4] 以 not given 为溶剂， 生成 [Rh(PCy3)2H2(η2-H2B=NMe2)][B(C6H3(CF3)2)4] 、 [Rh(PCy3)2H2(η2-H3BNMe2H)][B(C6H3(CF3)2)4] 、 [Rh(PCy3)2H2(η2-H3BNMe2BH2Me2H)][B(C6H3(CF3)2)4]
  参考文献：
  名称：

  Development of a Generic Mechanism for the Dehydrocoupling of Amine-Boranes: A Stoichiometric, Catalytic, and Kinetic Study of H₃B·NMe₂H Using the [Rh(PCy₃)₂]⁺ Fragment

  摘要：

  The multistage Rh-catalyzed dehydrocoupling of the secondary amine-borane H3B center dot NMe2H, to give the cyclic amino-borane [H2BNMe2](2), has been explored using catalysts based upon cationic [Rh(PCy3)(2)](+) (Cy = cyclo-C6H11). These were systematically investigated (NMR/MS), under both stoichiometric and catalytic regimes, with the resulting mechanistic proposals for parallel catalysis and autocatalysis evaluated by kinetic simulation. These studies demonstrate a rich and complex mechanistic landscape that involves dehydrogenation of H3B center dot NMe2H to give the amino-borane H2B = NMe2, dimerization of this to give the final product, formation of the linear diborazane H3B center dot NMe2BH2 center dot NMe2H as an intermediate, and its consumption by both B-N bond cleavage and dehydrocyclization. Subtleties of the system include the following: the product [H2BNMe2](2) is a modifier in catalysis and acts in an autocatalytic role; there is a parallel, neutral catalyst present in low but constant concentration, suggested to be Rh(PCy3)(2)H2Cl; the dimerization of H2B = NMe2 can be accelerated by MeCN; and complementary nonclassical BH center dot center dot center dot HN interactions are likely to play a role in lowering barriers to many of the processes occurring at the metal center. These observations lead to a generic mechanistic scheme that can be readily tailored for application to many of the transition-metal and main-group systems that catalyze the dehydrocoupling of H3B center dot NMe2H.

  DOI：

  10.1021/ja2112965