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Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide

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posted on 2019-10-02, 15:27 authored by Étienne Rochette, Marc-André Courtemanche, Alexander P. Pulis, Wenhua Bi, Frédéric-Georges Fontaine
The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

Funding

The authors would like to acknowledge National Sciences and Engineering Research Council of Canada (NSERC, Canada) and the Centre de Catalyse et Chimie Verte (Quebec) for financial support. M.-A.C. and E.R. would like to thank NSERC and FQRNT for scholarships. We acknowledge D.W. Stephan for the discussions.

History

Citation

Molecules, 2015, 20 (7), pp. 11902-11914

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

  • VoR (Version of Record)

Published in

Molecules

Publisher

MDPI

eissn

1420-3049

Acceptance date

2015-06-19

Copyright date

2015

Available date

2019-10-02

Publisher version

https://www.mdpi.com/1420-3049/20/7/11902

Notes

The supplementary materials include the NMR and the FT-IR spectra of compounds synthesized, the DFT data and important crystallographic parameters. Crystallographic data have been deposited with CCDC (CCDC No. 1060045 for 1 and CCDC No. 10060046 for 2). These data can be obtained upon request from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, E-Mail: deposit@ccdc.cam.ac.uk, or via the internet at www.ccdc.cam.ac.uk. Supplementary materials can be accessed at: http://www.mdpi.com/1420-3049/20/07/11902/s1.

Language

en

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