Allosteric Differentiation of Al(I) Reactivity

Han-Ying Liu; Jakub Kenar; Henry T. W. Shere; Ryan Schwamm; Michael S. Hill; Mary F. Mahon; Claire L. McMullin

doi:10.1002/chem.202501352

Allosteric Differentiation of Al(I) Reactivity

Han-Ying Liu, Jakub Kenar, Henry T. W. Shere, Ryan Schwamm, Michael S. Hill, Mary F. Mahon, Claire L. McMullin

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

Abstract

The dimeric potassium alumanyl, [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3), reacts with two equivalents of PhC≡CR (R = Ph or SiMe3) with the exclusive formation of the aluminacyclopropene derivatives, [{SiNDipp}Al{η2-C2(R1)(R2)}]. In contrast, reactions with an equal stoichiometry of both alumanyl and alkyne reagents provide the products of not only alkyne cycloaddition but also para-C–H activation of a phenyl substituent. Supported by a theoretical study, this outcome is judged to result from a sequence of cooperative steps and the introduction of a modicum of kinetic discrimination that is suggested to be allosteric in origin.

Original language	English
Article number	e202501352
Number of pages	7
Journal	Chemistry - A European Journal
Early online date	10 Apr 2025
DOIs	https://doi.org/10.1002/chem.202501352
Publication status	E-pub ahead of print - 10 Apr 2025

Data Availability Statement

The data that support the findings of this study are available inthe supporting information of this article

Funding

We acknowledge financial support from the EPSRC (research grant EP/R020752/1), the University of Bath (PhD studentship, HTWS) and the Royal Commission for the Exhibition of 1851 for the provision of a Postdoctoral Fellowship (RJS). We thank the University of Bath's Research Computing Group (doi.org/10.15125/b6cd\u2010s854) for their support in this work.

Funders	Funder number
University of Bath
Royal Commission for the Exhibition of 1851
Engineering and Physical Sciences Research Council	EP/R020752/1

Keywords

alkyne
aluminum
arene activation
cycloaddition
density functional theory

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

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10.1002/chem.202501352Licence: CC BY

Cite this

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title = "Allosteric Differentiation of Al(I) Reactivity",

abstract = "The dimeric potassium alumanyl, [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3), reacts with two equivalents of PhC≡CR (R = Ph or SiMe3) with the exclusive formation of the aluminacyclopropene derivatives, [{SiNDipp}Al{η2-C2(R1)(R2)}]. In contrast, reactions with an equal stoichiometry of both alumanyl and alkyne reagents provide the products of not only alkyne cycloaddition but also para-C–H activation of a phenyl substituent. Supported by a theoretical study, this outcome is judged to result from a sequence of cooperative steps and the introduction of a modicum of kinetic discrimination that is suggested to be allosteric in origin.",

keywords = "alkyne, aluminum, arene activation, cycloaddition, density functional theory",

author = "Han-Ying Liu and Jakub Kenar and Shere, {Henry T. W.} and Ryan Schwamm and Hill, {Michael S.} and Mahon, {Mary F.} and McMullin, {Claire L.}",

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journal = "Chemistry - A European Journal",

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T1 - Allosteric Differentiation of Al(I) Reactivity

AU - Liu, Han-Ying

AU - Kenar, Jakub

AU - Shere, Henry T. W.

AU - Schwamm, Ryan

AU - Hill, Michael S.

AU - Mahon, Mary F.

AU - McMullin, Claire L.

PY - 2025/4/10

Y1 - 2025/4/10

N2 - The dimeric potassium alumanyl, [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3), reacts with two equivalents of PhC≡CR (R = Ph or SiMe3) with the exclusive formation of the aluminacyclopropene derivatives, [{SiNDipp}Al{η2-C2(R1)(R2)}]. In contrast, reactions with an equal stoichiometry of both alumanyl and alkyne reagents provide the products of not only alkyne cycloaddition but also para-C–H activation of a phenyl substituent. Supported by a theoretical study, this outcome is judged to result from a sequence of cooperative steps and the introduction of a modicum of kinetic discrimination that is suggested to be allosteric in origin.

AB - The dimeric potassium alumanyl, [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3), reacts with two equivalents of PhC≡CR (R = Ph or SiMe3) with the exclusive formation of the aluminacyclopropene derivatives, [{SiNDipp}Al{η2-C2(R1)(R2)}]. In contrast, reactions with an equal stoichiometry of both alumanyl and alkyne reagents provide the products of not only alkyne cycloaddition but also para-C–H activation of a phenyl substituent. Supported by a theoretical study, this outcome is judged to result from a sequence of cooperative steps and the introduction of a modicum of kinetic discrimination that is suggested to be allosteric in origin.

KW - alkyne

KW - aluminum

KW - arene activation

KW - cycloaddition

KW - density functional theory

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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ER -

Allosteric Differentiation of Al(I) Reactivity

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

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Nucleophilic alkaline earth boryls: from conception and theory to application

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Allosteric Differentiation of Al(I) Reactivity

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Nucleophilic alkaline earth boryls: from conception and theory to application

Cite this