Reducing CO2 to Methanol Using Frustrated Lewis Pairs: On the Mechanism of Phosphine–Borane-Mediated Hydroboration of CO2

The full mechanism of the hydroboration of CO2 by the highly active ambiphilic organocatalyst 1-Bcat-2-PPh2–C6H4 (Bcat = catecholboryl) was determined using computational and experimental methods. The intramolecular Lewis pair was shown to be involved in every step of the stepwise reduction. In cont...

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Published in:Journal of the American Chemical Society 2014-07, Vol.136 (30), p.10708-10717
Main Authors: Courtemanche, Marc-André, Légaré, Marc-André, Maron, Laurent, Fontaine, Frédéric-Georges
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container_issue 30
container_start_page 10708
container_title Journal of the American Chemical Society
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creator Courtemanche, Marc-André
Légaré, Marc-André
Maron, Laurent
Fontaine, Frédéric-Georges
description The full mechanism of the hydroboration of CO2 by the highly active ambiphilic organocatalyst 1-Bcat-2-PPh2–C6H4 (Bcat = catecholboryl) was determined using computational and experimental methods. The intramolecular Lewis pair was shown to be involved in every step of the stepwise reduction. In contrast to traditional frustrated Lewis pair systems, the lack of steric hindrance around the Lewis basic fragment allows activation of the reducing agent while moderate Lewis acidity/basicity at the active centers promotes catalysis by releasing the reduction products. Simultaneous activation of both the reducing agent and carbon dioxide is the key to efficient catalysis in every reduction step.
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title Reducing CO2 to Methanol Using Frustrated Lewis Pairs: On the Mechanism of Phosphine–Borane-Mediated Hydroboration of CO2
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