Mechanism of the catalytic Carboxylation of alkylboronates with CO2 using Ni−NHC complexes: a DFT study

Delarmelina, Maicon ORCID: https://orcid.org/0000-0002-6414-552X, Marelli, Enrico, de M.Carneiro, José Walkimar, Nolan, Steven P. and Bühl, Michael 2017. Mechanism of the catalytic Carboxylation of alkylboronates with CO2 using Ni−NHC complexes: a DFT study. Chemistry - A European Journal 23 (59) , pp. 14954-14961. 10.1002/chem.201703567

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Abstract

A new mechanism is proposed for the Ni‐catalyzed carboxylation of organoboronates with CO2. DFT investigations at the PBE0‐D3 level have shown that direct CO2 addition to the catalysts [Ni(NHC)(Allyl)Cl] (1NHC, NHC=IMe, IPr, SIPr and IPr*) is kinetically disfavored and formation of the Aresta‐type intermediate is unlikely to occur. According to the mechanism proposed here, the carboxylation process starts with addition of the borate species to 1NHC, followed by transmetalation, CO2 cycloaddition and carboxylation. The rate‐determining step was identified as being the transmetalation process, with computed relative free energy barriers of 34.8, 36.8, and 33.5 kcal mol−1 for 1IPr, 1SIPr and 1IPr*, respectively.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Wiley
ISSN:	0947-6539
Last Modified:	04 Nov 2022 12:13
URI:	https://orca.cardiff.ac.uk/id/eprint/122287

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