St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  • Register / Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Mechanism of the catalytic carboxylation of alkylboronates with CO2 using Ni-NHC complexes : a DFT study

Thumbnail
View/Open
Buehl_2017_CAEJ_MechanismNi_NCH_AAM.pdf (2.147Mb)
Date
20/10/2017
Author
Delarmelina, Maicon
Marelli, Enrico
Carneiro, Jose
Nolan, Steven
Buehl, Michael
Funder
EPSRC
European Research Council
Grant ID
EP/K014854/1
FP7-227817 FUNCAT
Keywords
Carbene ligands
Nickel
N-Heterocyclic carbene
Carbon dioxide
Carboxylation
DFT
QD Chemistry
DAS
Metadata
Show full item record
Abstract
A new mechanism is proposed for the Ni-catalysed 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
Citation
Delarmelina , M , Marelli , E , Carneiro , J , Nolan , S & Buehl , M 2017 , ' Mechanism of the catalytic carboxylation of alkylboronates with CO 2 using Ni-NHC complexes : a DFT study ' , Chemistry - A European Journal , vol. 23 , no. 59 , pp. 14954-14961 . https://doi.org/10.1002/chem.201703567
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201703567
ISSN
0947-6539
Type
Journal article
Rights
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/chem.201703567
Description
The authors acknowledge FAPERJ for providing research grants and financial support. MB thanks the School of Chemistry and EaStCHEM for support and for access to a computer cluster maintained by Dr H. Früchtl. JWMC acknowledges CNPq for a research grant. The experimental work was supported via our membership of the UK Catalysis Hub consortium funded by EPSRC (grants EP/K014706/2, EP/K014668/1, EP/K014854/1 and EP/K014714/1). SPN gratefully acknowledges the European Commission for support in the form of an ERC Advanced Researcher grant (227817-FUNCAT).
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/16107

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter