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

Maicon Delarmelina; Enrico Marelli; Jose Carneiro; Steven Nolan; Michael Buehl

doi:10.1002/chem.201703567

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

Maicon Delarmelina, Enrico Marelli, Jose Carneiro, Steven Nolan, Michael Buehl

Research output: Contribution to journal › Article › peer-review

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] (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, 1S_IPr and 1_IPr*, respectively

Original language	English
Pages (from-to)	14954-14961
Journal	Chemistry - A European Journal
Volume	23
Issue number	59
Early online date	26 Sept 2017
DOIs	https://doi.org/10.1002/chem.201703567
Publication status	Published - 20 Oct 2017

Keywords

Carbene ligands
Nickel
N-Heterocyclic carbene
Carbon dioxide
Carboxylation
DFT

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10.1002/chem.201703567

Buehl_2017_CAEJ_MechanismNi-NCH_AAM
© 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
Accepted author manuscript, 2.15 MB

UK Catalysis Hub: The UK Catalysis Hub
Nolan, S. P. (PI)
EPSRC
1/10/13 → 31/05/18
Project: Standard
FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis
Nolan, S. P. (PI)
European Research Council
1/01/09 → 31/12/14
Project: Standard

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO2 using Ni-NHC complexes: A DFT Study (dataset)
Delarmelina, M. (Creator), Marelli, E. (Creator), Carneiro, J. (Creator), Nolan, S. (Creator) & Buehl, M. (Creator), University of St Andrews, 9 Oct 2017
DOI: 10.17630/383e38ec-a571-49ca-8a54-9ebf020e4513
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Cite this

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

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",

keywords = "Carbene ligands, Nickel, N-Heterocyclic carbene, Carbon dioxide, Carboxylation, DFT",

author = "Maicon Delarmelina and Enrico Marelli and Jose Carneiro and Steven Nolan and Michael Buehl",

note = "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. Fr{\"u}chtl. 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).",

year = "2017",

month = oct,

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doi = "10.1002/chem.201703567",

language = "English",

volume = "23",

pages = "14954--14961",

journal = "Chemistry - A European Journal",

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publisher = "John Wiley & Sons, Ltd",

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TY - JOUR

T1 - Mechanism of the catalytic carboxylation of alkylboronates with CO2 using Ni-NHC complexes

T2 - a DFT study

AU - Delarmelina, Maicon

AU - Marelli, Enrico

AU - Carneiro, Jose

AU - Nolan, Steven

AU - Buehl, Michael

N1 - 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).

PY - 2017/10/20

Y1 - 2017/10/20

N2 - 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

AB - 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

KW - Carbene ligands

KW - Nickel

KW - N-Heterocyclic carbene

KW - Carbon dioxide

KW - Carboxylation

KW - DFT

U2 - 10.1002/chem.201703567

DO - 10.1002/chem.201703567

M3 - Article

SN - 0947-6539

VL - 23

SP - 14954

EP - 14961

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 59

ER -

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

Abstract

Keywords

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Projects

UK Catalysis Hub: The UK Catalysis Hub

FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis

Datasets

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO2 using Ni-NHC complexes: A DFT Study (dataset)

Cite this

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