Hydridostannylene Derivatives of Magnesium and Calcium

Dominic B. Kennedy; Kyle G. Pearce; Samuel E. Neale; Louis J. Morris; Mary F. Mahon; John P. Lowe; Claire L. McMullin; Cameron Jones; Michael S. Hill

doi:10.1002/chem.202404416

Hydridostannylene Derivatives of Magnesium and Calcium

Dominic B. Kennedy, Kyle G. Pearce, Samuel E. Neale, Louis J. Morris, Mary F. Mahon, John P. Lowe, Claire L. McMullin, Cameron Jones, Michael S. Hill

Monash University

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

Abstract

Reactions of a m-terphenylhydridostannylene with β-diketiminato magnesium and calcium hydrides provide bis-μ2-hydrido species, the heterobimetallic constitutions of which are maintained after the addition of THF donor solvent. In both cases, reactions with hex-1-ene result in the formation of tetravalent organostannyl alkaline earth derivatives. Whereas the magnesium reagent undergoes facile twofold addition, the calcium-centered process is arrested after a single alkene reduction event. This contrasting behavior is assessed to result from the heavier alkaline earth element's ability to form a persistent polyhapto interaction with an arene substituent of the m-terphenyl ligand.

Original language	English
Article number	e202404416
Journal	Chemistry - A European Journal
Volume	31
Issue number	10
Early online date	2 Dec 2024
DOIs	https://doi.org/10.1002/chem.202404416
Publication status	Published - 17 Feb 2025

Data Availability Statement

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

Funding

We thank the EPSRC (EP/X01181X/1) and the University of Bath's Research Computing Group (DOI: 10.15125/b6cd\u2010s854 ) for their support in this work. This work also used the Isambard 2 UK National Tier\u20102 HPC Service ( http://gw4.ac.uk/isambard/ ) operated by GW4 and the UK Met Office, and funded by EPSRC (EP/T022078/1). DBK thanks the joint Bath/Monash PhD program for funding. CJ is grateful to the Australian Research Council and the US Air Force Asian Office of Aerospace Research and Development (grant FA2386\u201021\u20101\u20104048) for funding this work.

Funders	Funder number
The Met Office
Australian Research Council
Engineering and Physical Sciences Research Council	EP/T022078/1
Engineering and Physical Sciences Research Council
US Air Force Asian Office of Aerospace Research and Development	FA2386‐21‐1‐4048

Keywords

Calcium
Density functional theory
Hydride
Magnesium
Stannylene

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

Access to Document

10.1002/chem.202404416Licence: CC BY

Cite this

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abstract = "Reactions of a m-terphenylhydridostannylene with β-diketiminato magnesium and calcium hydrides provide bis-μ2-hydrido species, the heterobimetallic constitutions of which are maintained after the addition of THF donor solvent. In both cases, reactions with hex-1-ene result in the formation of tetravalent organostannyl alkaline earth derivatives. Whereas the magnesium reagent undergoes facile twofold addition, the calcium-centered process is arrested after a single alkene reduction event. This contrasting behavior is assessed to result from the heavier alkaline earth element's ability to form a persistent polyhapto interaction with an arene substituent of the m-terphenyl ligand.",

keywords = "Calcium, Density functional theory, Hydride, Magnesium, Stannylene",

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AU - Kennedy, Dominic B.

AU - Pearce, Kyle G.

AU - Neale, Samuel E.

AU - Morris, Louis J.

AU - Mahon, Mary F.

AU - Lowe, John P.

AU - McMullin, Claire L.

AU - Jones, Cameron

AU - Hill, Michael S.

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N2 - Reactions of a m-terphenylhydridostannylene with β-diketiminato magnesium and calcium hydrides provide bis-μ2-hydrido species, the heterobimetallic constitutions of which are maintained after the addition of THF donor solvent. In both cases, reactions with hex-1-ene result in the formation of tetravalent organostannyl alkaline earth derivatives. Whereas the magnesium reagent undergoes facile twofold addition, the calcium-centered process is arrested after a single alkene reduction event. This contrasting behavior is assessed to result from the heavier alkaline earth element's ability to form a persistent polyhapto interaction with an arene substituent of the m-terphenyl ligand.

AB - Reactions of a m-terphenylhydridostannylene with β-diketiminato magnesium and calcium hydrides provide bis-μ2-hydrido species, the heterobimetallic constitutions of which are maintained after the addition of THF donor solvent. In both cases, reactions with hex-1-ene result in the formation of tetravalent organostannyl alkaline earth derivatives. Whereas the magnesium reagent undergoes facile twofold addition, the calcium-centered process is arrested after a single alkene reduction event. This contrasting behavior is assessed to result from the heavier alkaline earth element's ability to form a persistent polyhapto interaction with an arene substituent of the m-terphenyl ligand.

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KW - Density functional theory

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KW - Stannylene

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Hydridostannylene Derivatives of Magnesium and Calcium

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

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

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Hydridostannylene Derivatives of Magnesium and Calcium

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

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