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Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products

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Abstract

The present study details the use of the acetate anion, an inexpensive and robust anion, as a CO2 hydroboration catalyst for the selective formation, in most cases, of methanol-equivalent borane products. Thus, upon heating (90 °C, PhBr), tetrabutylammonium, sodium and potassium acetate (1, 2 and 3, respectively) effectively catalyze CO2 hydroboration by pinacolborane (pinB–H) to afford CO2 reduction products HOCOBpin (A), pinBOCH2OBpin (B) and methoxyborane (C). In most cases, high selectivity for product C with higher borane loading and longer reaction time with a TON of up to 970 was observed. The reduction catalysis remains efficient at low catalyst loading (down to 0.1 mol%) and may also be performed under solvent-free conditions using salt 1 as a catalyst, reflecting the excellent robustness and stability of the acetate anion. In control experiments, a 1/1 1/pinB–H mixture was found to react fast with CO2 at room temperature to produce formate species [pinB(O2CH)(OAc)][N(nBu)4] (5) through CO2 insertion into the B–H bond. DFT calculations were also performed to gain insight into the acetate-mediated CO2 hydroboration catalysis, which further supported the crucial role of acetate as a Lewis base in CO2 functionalization catalysis by pinB–H. The DFT-estimated mechanism is in line with experimental data and rationalizes the formation of the most thermodynamically stable reduction product C through acetate catalysis.

Graphical abstract: Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products

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Supplementary files

Article information


Submitted
19 Jan 2020
Accepted
17 Mar 2020
First published
21 Mar 2020

Catal. Sci. Technol., 2020, Advance Article
Article type
Paper

Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products

Y. C. A. Sokolovicz, O. Nieto Faza, D. Specklin, B. Jacques, C. S. López, J. H. Z. dos Santos, H. S. Schrekker and S. Dagorne, Catal. Sci. Technol., 2020, Advance Article , DOI: 10.1039/D0CY00118J

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