4.7 Article

Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide

期刊

INORGANIC CHEMISTRY
卷 60, 期 7, 页码 4569-4577

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03507

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资金

  1. National Research Foundation Singapore
  2. NRF-ANR [NRF2018-NRF-ANR026 Si-POP]
  3. Ministry of Education Singapore [MOE2019-T2-2-129, RG 17/17]

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This study presents the first use of a bis(phosphoranyl) methanido aluminum hydride for the catalytic hydroboration of CO2. The complex showed good catalytic activity towards various substrates, demonstrating high efficiency in the reduction reactions.
This study describes the first use of a bis(phosphoranyl) methanido aluminum hydride, [ClC(PPh(2)NMes)(2)AlH2] (2, Mes = Me3C6H2), for the catalytic hydroboration of CO2. Complex 2 was synthesized by the reaction of a lithium carbenoid [Li(Cl)C(PPh(2)NMes)(2)] with 2 equiv of AlH3 center dot NEtMe2 in toluene at -78 degrees C. 2 (10 mol %) was able to catalyze the reduction of CO2 with HBpin in C6D6 at 110 degrees C for 2 days to afford a mixture of methoxyborane [MeOBpin] (3a; yield: 78%, TOF: 0.16 h(-1)) and bis(boryl)oxide [pinBOBpin] (3b). When more potent [BH3 center dot SMe2] was used instead of HBpin, the catalytic reaction was extremely pure, resulting in the formation of trimethyl borate [B(OMe)(3)] (3e) [catalytic loading: 1 mol % (10 mol %); reaction time: 60 min (5 min); yield: 97.6% (>99%); TOF: 292.8 h(-1) (356.4 h(-1))] and B2O3 (3f). Mechanistic studies show that the Al-H bond in complex 2 activated CO2 to form [ClC(PPh(2)NMes)(2)Al(H){OC(O)H}] (4), which was subsequently reacted with BH3 center dot SMe2 to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity toward the hydroboration of carbonyl, nitrile, and alkyne derivatives.

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