An Alumanyl Test Case of Group 1 Redox Interchange

Kyle Pearce; Agustin Morales Aguilar; Michael Hill; Claire McMullin

doi:10.1002/chem.202502197

An Alumanyl Test Case of Group 1 Redox Interchange

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5 Citations (SciVal)

Abstract

Rationalized by a thermochemical evaluation using both theoretical density functional theory (DFT) and empirical data, we show that the arene-encapsulated M+ cations of the group 1 alumanyls, [{SiNDipp}AlM]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3); M = Li, Na, K, Rb, Cs] may be interconverted by redox reactions with the elemental alkali metals. These observations contradict the established E0 data and allow access to an otherwise inaccessible sodium derivative.

Original language	English
Article number	e202502197
Journal	Chemistry - A European Journal
Volume	31
Issue number	44
Early online date	8 Jul 2025
DOIs	https://doi.org/10.1002/chem.202502197
Publication status	Published - 7 Aug 2025

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

Acknowledgements

The authors acknowledge EPSRC (EP/X01181X/1, “Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements”) and the University of Bath's Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.

Funding

The authors acknowledge EPSRC (EP/X01181X/1, \u201CMolecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements\u201D) and the University of Bath's Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.

Funders	Funder number
University of Bath
Engineering and Physical Sciences Research Council	EP/X01181X/1

Keywords

alumanyl
cesium
density functional theory
lithium
potassium
rubidium
sodium

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10.1002/chem.202502197Licence: CC BY

Cite this

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title = "An Alumanyl Test Case of Group 1 Redox Interchange",

abstract = "Rationalized by a thermochemical evaluation using both theoretical density functional theory (DFT) and empirical data, we show that the arene-encapsulated M+ cations of the group 1 alumanyls, [\{SiNDipp\}AlM]2 (\{SiNDipp\} = \{CH2SiMe2N(Dipp)\}2; Dipp = 2,6-i-Pr2C6H3); M = Li, Na, K, Rb, Cs] may be interconverted by redox reactions with the elemental alkali metals. These observations contradict the established E0 data and allow access to an otherwise inaccessible sodium derivative.",

keywords = "alumanyl, cesium, density functional theory, lithium, potassium, rubidium, sodium",

author = "Kyle Pearce and \{Morales Aguilar\}, Agustin and Michael Hill and Claire McMullin",

year = "2025",

month = aug,

day = "7",

doi = "10.1002/chem.202502197",

language = "English",

volume = "31",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

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TY - JOUR

T1 - An Alumanyl Test Case of Group 1 Redox Interchange

AU - Pearce, Kyle

AU - Morales Aguilar, Agustin

AU - Hill, Michael

AU - McMullin, Claire

PY - 2025/8/7

Y1 - 2025/8/7

N2 - Rationalized by a thermochemical evaluation using both theoretical density functional theory (DFT) and empirical data, we show that the arene-encapsulated M+ cations of the group 1 alumanyls, [{SiNDipp}AlM]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3); M = Li, Na, K, Rb, Cs] may be interconverted by redox reactions with the elemental alkali metals. These observations contradict the established E0 data and allow access to an otherwise inaccessible sodium derivative.

AB - Rationalized by a thermochemical evaluation using both theoretical density functional theory (DFT) and empirical data, we show that the arene-encapsulated M+ cations of the group 1 alumanyls, [{SiNDipp}AlM]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3); M = Li, Na, K, Rb, Cs] may be interconverted by redox reactions with the elemental alkali metals. These observations contradict the established E0 data and allow access to an otherwise inaccessible sodium derivative.

KW - alumanyl

KW - cesium

KW - density functional theory

KW - lithium

KW - potassium

KW - rubidium

KW - sodium

UR - https://www.scopus.com/pages/publications/105011353187

U2 - 10.1002/chem.202502197

DO - 10.1002/chem.202502197

M3 - Article

SN - 0947-6539

VL - 31

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 44

M1 - e202502197

ER -

An Alumanyl Test Case of Group 1 Redox Interchange

Abstract

Data Availability Statement

Acknowledgements

Funding

Keywords

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Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Cite this

An Alumanyl Test Case of Group 1 Redox Interchange

Abstract

Data Availability Statement

Acknowledgements

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Projects

Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Cite this