Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)2] to form unsupported Ni-boryls

Gabrielle Audsley; Ambre Carpentier; Anne-Frédérique Pécharman; James Wright; Thomas M. Roseveare; Ewan R. Clark; Stuart A. Macgregor; Ian M. Riddlestone

doi:10.1039/d3cc05369e

Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)₂] to form unsupported Ni-boryls

Gabrielle Audsley, Ambre Carpentier, Anne-Frédérique Pécharman, James Wright, Thomas M. Roseveare, Ewan R. Clark, Stuart A. Macgregor^*, Ian M. Riddlestone^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

[Ni(IMes)₂] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B–Cl activation proceeds via nucleophilic displacement of Cl⁻, while B–H activation would entail high energy concerted bond cleavage.

Original language	English
Pages (from-to)	874-877
Number of pages	4
Journal	Chemical Communications
Volume	60
Issue number	7
DOIs	https://doi.org/10.1039/d3cc05369e
Publication status	Published - 21 Jan 2024

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Audsley_2023_CC_Contrasting-reactivity-[Ni(IMes)2]-Ni-boryls_CC
© 2024 The Author(s). This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (https://creativecommons.org/licenses/by/3.0/).
Final published version, 820 KBLicence: CC BY

CCDC 2304313 -2304318: Experimental Crystal Structure Determination
Audsley, G. (Creator), Carpentier, A. (Creator), Pécharman, A.-F. (Creator), Wright, J. (Creator), Roseveare, T. M. (Creator), Clark, E. R. (Creator), Macgregor, S. A. (Creator) & Riddlestone, I. M. (Creator), Cambridge Crystallographic Data Centre, 2024
DOI: 10.5517/ccdc.csd.cc2hbtpc, https://dx.doi.org/10.5517/ccdc.csd.cc2hbtqd and 4 more links, https://dx.doi.org/10.5517/ccdc.csd.cc2hbtrf, https://dx.doi.org/10.5517/ccdc.csd.cc2hbtsg, https://dx.doi.org/10.5517/ccdc.csd.cc2hbtth, https://dx.doi.org/10.5517/ccdc.csd.cc2hbtvj (show fewer)
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title = "Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)2] to form unsupported Ni-boryls",

abstract = "[Ni(IMes)2] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B–Cl activation proceeds via nucleophilic displacement of Cl−, while B–H activation would entail high energy concerted bond cleavage.",

author = "Gabrielle Audsley and Ambre Carpentier and Anne-Fr{\'e}d{\'e}rique P{\'e}charman and James Wright and Roseveare, {Thomas M.} and Clark, {Ewan R.} and Macgregor, {Stuart A.} and Riddlestone, {Ian M.}",

note = "Funding: G. A. thanks the University of Surrey for a studentship. I. M. R. thanks the Royal Society of Chemistry for support (R21-1723146519). A. C. thanks Heriot-Watt University for a James Watt Scholarship.",

year = "2024",

month = jan,

day = "21",

doi = "10.1039/d3cc05369e",

language = "English",

volume = "60",

pages = "874--877",

journal = "Chemical Communications",

issn = "1359-7345",

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T1 - Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)2] to form unsupported Ni-boryls

AU - Audsley, Gabrielle

AU - Carpentier, Ambre

AU - Pécharman, Anne-Frédérique

AU - Wright, James

AU - Roseveare, Thomas M.

AU - Clark, Ewan R.

AU - Macgregor, Stuart A.

AU - Riddlestone, Ian M.

N1 - Funding: G. A. thanks the University of Surrey for a studentship. I. M. R. thanks the Royal Society of Chemistry for support (R21-1723146519). A. C. thanks Heriot-Watt University for a James Watt Scholarship.

PY - 2024/1/21

Y1 - 2024/1/21

N2 - [Ni(IMes)2] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B–Cl activation proceeds via nucleophilic displacement of Cl−, while B–H activation would entail high energy concerted bond cleavage.

AB - [Ni(IMes)2] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B–Cl activation proceeds via nucleophilic displacement of Cl−, while B–H activation would entail high energy concerted bond cleavage.

U2 - 10.1039/d3cc05369e

DO - 10.1039/d3cc05369e

M3 - Article

C2 - 38164828

SN - 1359-7345

VL - 60

SP - 874

EP - 877

JO - Chemical Communications

JF - Chemical Communications

IS - 7

ER -

Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)2] to form unsupported Ni-boryls

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CCDC 2304313 -2304318: Experimental Crystal Structure Determination

Cite this

Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)₂] to form unsupported Ni-boryls