1,4-Dialumination of benzene by sodium and potassium aluminyls

Andrea O'Reilly; Andrew Booth; Claire McMullin; Robin Fulton; Martyn Coles

doi:10.1016/j.poly.2024.117226

1,4-Dialumination of benzene by sodium and potassium aluminyls

Andrea O'Reilly, Andrew Booth, Claire McMullin, Robin Fulton, Martyn Coles

Department of Chemistry

Victoria University of Wellington

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

Abstract

Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.

Original language	English
Article number	117226
Journal	Polyhedron
Volume	264
Early online date	17 Sept 2024
DOIs	https://doi.org/10.1016/j.poly.2024.117226
Publication status	E-pub ahead of print - 17 Sept 2024

Data Availability Statement

Data will be made available on request.

Acknowledgements

The authors also gratefully acknowledge the University of Bath's Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.

Keywords

1,4-Dialumination
Aluminyl
C-H activation
Inverse sandwich
Oxidative addition

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2024.117226Licence: CC BY

Cite this

@article{ca016dd78a9f4a849c50f58c4ed0f3fc,

title = "1,4-Dialumination of benzene by sodium and potassium aluminyls",

abstract = "Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the {\textquoteright}Al(NON)(H){\textquoteright} groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.",

keywords = "1,4-Dialumination, Aluminyl, C-H activation, Inverse sandwich, Oxidative addition",

author = "Andrea O'Reilly and Andrew Booth and Claire McMullin and Robin Fulton and Martyn Coles",

year = "2024",

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language = "English",

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journal = "Polyhedron",

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T1 - 1,4-Dialumination of benzene by sodium and potassium aluminyls

AU - O'Reilly, Andrea

AU - Booth, Andrew

AU - McMullin, Claire

AU - Fulton, Robin

AU - Coles, Martyn

PY - 2024/9/17

Y1 - 2024/9/17

N2 - Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.

AB - Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.

KW - 1,4-Dialumination

KW - Aluminyl

KW - C-H activation

KW - Inverse sandwich

KW - Oxidative addition

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M3 - Article

SN - 0277-5387

VL - 264

JO - Polyhedron

JF - Polyhedron

M1 - 117226

ER -

1,4-Dialumination of benzene by sodium and potassium aluminyls

Abstract

Data Availability Statement

Acknowledgements

Keywords

ASJC Scopus subject areas

Access to Document

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Anatra HTC cluster

Cite this

1,4-Dialumination of benzene by sodium and potassium aluminyls

Abstract

Data Availability Statement

Acknowledgements

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

Anatra HTC cluster

Cite this