Implications of CO2 Activation by Frustrated Lewis Pairs in the Catalytic Hydroboration of CO2 : A View Using N/Si + Frustrated Lewis Pairs

N Von Wolff 1 G Lefèvre 1 J.-C Berthet 1 Pierre Thuéry 1 T Cantat 1
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : A series of base-stabilized silylium species were synthesized and their reactivity toward CO 2 explored, yielding the characterization of a novel N/ Si + FLP-CO 2 adduct. These silicon species are active catalysts in the hydroboration of CO 2 to the methoxide level with 9-BBN, catecholborane (catBH), and pinacolborane (pinBH). Both experiments and DFT calculations highlight the role of the FLP-CO 2 adduct in the catalysis. Depending on the nature of the hydroborane reductant, two distinct mechanisms have been unveiled. While 9-BBN and catBH are able to reduce an intermediate FLP-CO 2 adduct, the hydroboration of CO 2 with pinBH follows a different and novel path where the B−H bond is activated by the silicon-based Lewis acid catalyst. In these mechanisms, the formation of a highly stabilized FLP-CO 2 adduct is found detrimental to the kinetics of the reaction.
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ACS Catalysis, American Chemical Society, 2016, 6, pp.4526-4535. 〈http://dx.doi.org/10.1021/acscatal.6b00421〉. 〈10.1021/acscatal.6b00421〉
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Soumis le : mercredi 30 janvier 2019 - 12:37:22
Dernière modification le : jeudi 7 février 2019 - 17:03:03

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N Von Wolff, G Lefèvre, J.-C Berthet, Pierre Thuéry, T Cantat. Implications of CO2 Activation by Frustrated Lewis Pairs in the Catalytic Hydroboration of CO2 : A View Using N/Si + Frustrated Lewis Pairs. ACS Catalysis, American Chemical Society, 2016, 6, pp.4526-4535. 〈http://dx.doi.org/10.1021/acscatal.6b00421〉. 〈10.1021/acscatal.6b00421〉. 〈cea-01338153〉

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