Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 59, Pages 14954-14961Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201703567
Keywords
carbon dioxide; carboxylation; density functional calculations; N-heterocyclic carbenes; nickel
Categories
Funding
- FAPERJ
- CNPq
- EPSRC [EP/K014706/2, EP/K014668/1, EP/K014854/1, EP/K014714/1]
- European Commission [227817-FUNCAT]
- School of Chemistry
- EaStCHEM
- EPSRC [EP/K014854/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K014854/1] Funding Source: researchfish
Ask authors/readers for more resources
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] (1(NHC), 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 1(NHC), 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 1(IPr), 1(SIPr) and 1(IPr*), respectively.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available