Structural Diversity in Homoleptic Lithium Amidomanganate(II) Complexes: Impact of Amine Substitution

Marina Uzelac; Mary Mahon; Rebecca Jones

doi:10.1002/ejic.202400512

Structural Diversity in Homoleptic Lithium Amidomanganate(II) Complexes: Impact of Amine Substitution

Marina Uzelac, Mary Mahon, Rebecca Jones

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

Abstract

Expanding the library of structurally characterized lithium amidomanganates(II), here we report a general synthetic approach to access a new series of homoleptic complexes. In situ salt-metathesis of commercially available reagents afforded tetrabutyl lithium manganate [(TMEDA) ₂Li ₂Mn( ⁿBu) ₄] (1) (TMEDA=N,N,N’,N’-tetramethylethylendiamine) which could be used as a precursor for direct deprotonation of a selection of amines affording a family of homoleptic lithium amidomanganates. Complexes [{Li(THF) ₄} ⁺{Mn(NPh ₂) ₃(THF)} ^-] (2), [(THF)LiMn(NCy ₂) ₃] (3) (Cy=cyclohexyl), [(HNCy ₂)LiMn(NCy ₂) ₃] (4), [(THF) ₄Li ₂Mn(NHMes) ₄] (5) (Mes=2,4,6-trimethylphenyl), and [(TMEDA) ₂Li ₂Mn(NHMes) ₄] (6) have been isolated and structurally characterized as main products. While it is evident that 1 possesses adequate basicity to effect deprotonation of both primary and secondary amines, the exact stoichiometry, constitution, and structural motif of newly generated lithium amidomanganates are governed by the steric and electronic variations of the amide ligands.

Original language	English
Article number	e202400512
Number of pages	10
Journal	European Journal of Inorganic Chemistry
Volume	27
Issue number	36
Early online date	27 Nov 2024
DOIs	https://doi.org/10.1002/ejic.202400512
Publication status	Published - 20 Dec 2024

Data Availability Statement

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

Acknowledgements

We also thank Professors Eva Hevia and Michael S. Hill for their insightful comments.

Funding

We thank Royal Society (University Research Fellowship to M. U.) and University of Bath (PhD Studentship to R.S.J) for their generous funding of this research. We also thank Professors Eva Hevia and Michael S. Hill for their insightful comments.

Funders	Funder number
The Royal Society	URF\R1\221304, RF\ERE\221052
Royal Society
University of Bath

Keywords

Deprotonation
Lithium
Manganates
Metal amides
Structural elucidation

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Structural Diversity in Homoleptic Lithium Amidomanganate(II) Complexes: Impact of Amine Substitution",

abstract = "Expanding the library of structurally characterized lithium amidomanganates(II), here we report a general synthetic approach to access a new series of homoleptic complexes. In situ salt-metathesis of commercially available reagents afforded tetrabutyl lithium manganate [(TMEDA) 2Li 2Mn( nBu) 4] (1) (TMEDA=N,N,N{\textquoteright},N{\textquoteright}-tetramethylethylendiamine) which could be used as a precursor for direct deprotonation of a selection of amines affording a family of homoleptic lithium amidomanganates. Complexes [{Li(THF) 4} +{Mn(NPh 2) 3(THF)} -] (2), [(THF)LiMn(NCy 2) 3] (3) (Cy=cyclohexyl), [(HNCy 2)LiMn(NCy 2) 3] (4), [(THF) 4Li 2Mn(NHMes) 4] (5) (Mes=2,4,6-trimethylphenyl), and [(TMEDA) 2Li 2Mn(NHMes) 4] (6) have been isolated and structurally characterized as main products. While it is evident that 1 possesses adequate basicity to effect deprotonation of both primary and secondary amines, the exact stoichiometry, constitution, and structural motif of newly generated lithium amidomanganates are governed by the steric and electronic variations of the amide ligands.",

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N2 - Expanding the library of structurally characterized lithium amidomanganates(II), here we report a general synthetic approach to access a new series of homoleptic complexes. In situ salt-metathesis of commercially available reagents afforded tetrabutyl lithium manganate [(TMEDA) 2Li 2Mn( nBu) 4] (1) (TMEDA=N,N,N’,N’-tetramethylethylendiamine) which could be used as a precursor for direct deprotonation of a selection of amines affording a family of homoleptic lithium amidomanganates. Complexes [{Li(THF) 4} +{Mn(NPh 2) 3(THF)} -] (2), [(THF)LiMn(NCy 2) 3] (3) (Cy=cyclohexyl), [(HNCy 2)LiMn(NCy 2) 3] (4), [(THF) 4Li 2Mn(NHMes) 4] (5) (Mes=2,4,6-trimethylphenyl), and [(TMEDA) 2Li 2Mn(NHMes) 4] (6) have been isolated and structurally characterized as main products. While it is evident that 1 possesses adequate basicity to effect deprotonation of both primary and secondary amines, the exact stoichiometry, constitution, and structural motif of newly generated lithium amidomanganates are governed by the steric and electronic variations of the amide ligands.

AB - Expanding the library of structurally characterized lithium amidomanganates(II), here we report a general synthetic approach to access a new series of homoleptic complexes. In situ salt-metathesis of commercially available reagents afforded tetrabutyl lithium manganate [(TMEDA) 2Li 2Mn( nBu) 4] (1) (TMEDA=N,N,N’,N’-tetramethylethylendiamine) which could be used as a precursor for direct deprotonation of a selection of amines affording a family of homoleptic lithium amidomanganates. Complexes [{Li(THF) 4} +{Mn(NPh 2) 3(THF)} -] (2), [(THF)LiMn(NCy 2) 3] (3) (Cy=cyclohexyl), [(HNCy 2)LiMn(NCy 2) 3] (4), [(THF) 4Li 2Mn(NHMes) 4] (5) (Mes=2,4,6-trimethylphenyl), and [(TMEDA) 2Li 2Mn(NHMes) 4] (6) have been isolated and structurally characterized as main products. While it is evident that 1 possesses adequate basicity to effect deprotonation of both primary and secondary amines, the exact stoichiometry, constitution, and structural motif of newly generated lithium amidomanganates are governed by the steric and electronic variations of the amide ligands.

KW - Deprotonation

KW - Lithium

KW - Manganates

KW - Metal amides

KW - Structural elucidation

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Structural Diversity in Homoleptic Lithium Amidomanganate(II) Complexes: Impact of Amine Substitution

Abstract

Data Availability Statement

Acknowledgements

Funding

Keywords

ASJC Scopus subject areas

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