Well-defined Mn(I)-PNP pincer-type complexes were tested as non-precious transition metal catalysts for the selective reduction of CO2 to boryl-protected MeOH in the presence of hydroboranes (HBpin, 9-BBN) and borates as Lewis acids (LA) additives. The best performance was obtained under mild reaction conditions (1 bar CO2, 60 °C) in the presence of the hydridocarbonyl complex [MnH(PNPNH-iPr)(CO)2] and B(OPh)3 as co-catalyst. Preliminary mechanistic studies suggest that the initial activation step may occur by cationization of the metal center by the strong LA, and that both metal-catalyzed and metal-free steps are present in the overall catalytic system.
Mild and Selective Carbon Dioxide Hydroboration to Methoxyboranes Catalyzed by Mn(I) PNP Pincer Complexes
Kostera Sylwia;Peruzzini Maurizio;Gonsalvi Luca
2020
Abstract
Well-defined Mn(I)-PNP pincer-type complexes were tested as non-precious transition metal catalysts for the selective reduction of CO2 to boryl-protected MeOH in the presence of hydroboranes (HBpin, 9-BBN) and borates as Lewis acids (LA) additives. The best performance was obtained under mild reaction conditions (1 bar CO2, 60 °C) in the presence of the hydridocarbonyl complex [MnH(PNPNH-iPr)(CO)2] and B(OPh)3 as co-catalyst. Preliminary mechanistic studies suggest that the initial activation step may occur by cationization of the metal center by the strong LA, and that both metal-catalyzed and metal-free steps are present in the overall catalytic system.| File | Dimensione | Formato | |
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Descrizione: Mild and Selective Carbon Dioxide Hydroboration to Methoxyboranes Catalyzed by Mn(I) PNP Pincer Complexes
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cctc.202000469.pdf
Open Access dal 21/07/2021
Descrizione: "This is the peer reviewed version of the following article: S. Kostera, M. Peruzzini, K. Kirchner, L. Gonsalvi, ChemCatChem 2020, 12, 4625, which has been published in final form at https://doi.org/10.1002/cctc.202000469. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited."
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