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Mild and Selective Carbon Dioxide Hydroboration to Methoxyboranes Catalyzed by Mn(I) PNP Pincer Complexes
Author(s) -
Kostera Sylwia,
Peruzzini Maurizio,
Kirchner Karl,
Gonsalvi Luca
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202000469
Subject(s) - pincer movement , hydroboration , catalysis , chemistry , transition metal , medicinal chemistry , metal , lewis acids and bases , selective reduction , inorganic chemistry , organic chemistry
Abstract Well‐defined Mn(I)‐PNP pincer‐type complexes were tested as non‐precious transition metal catalysts for the selective reduction of CO 2 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 CO 2 , 60 °C) in the presence of the hydridocarbonyl complex [MnH(PNP NH – i Pr)(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.