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

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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
Early online date	18 Dec 2023
DOIs	https://doi.org/10.1039/d3cc05369e
Publication status	Published - 21 Jan 2024

Keywords

Materials Chemistry
Metals and Alloys
Surfaces, Coatings and Films
General Chemistry
Ceramics and Composites
Electronic, Optical and Magnetic Materials
Catalysis

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Metals and Alloys
Materials Chemistry
Surfaces, Coatings and Films
General Chemistry
Catalysis

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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.",

keywords = "Materials Chemistry, Metals and Alloys, Surfaces, Coatings and Films, General Chemistry, Ceramics and Composites, Electronic, Optical and Magnetic Materials, Catalysis",

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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.

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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.

KW - Materials Chemistry

KW - Metals and Alloys

KW - Surfaces, Coatings and Films

KW - General Chemistry

KW - Ceramics and Composites

KW - Electronic, Optical and Magnetic Materials

KW - Catalysis

UR - https://www.scopus.com/pages/publications/85181444092

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