A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies

Nathan Davison; Paul G. Waddell; Dixon Casey; Corinne Wills; Thomas J. Penfold; Erli Lu

doi:10.1039/D1DT03532K

A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies

Nathan Davison
, Paul G. Waddell
, Dixon Casey
, Corinne Wills
, Thomas J. Penfold^*
, Erli Lu^*

^*Corresponding author for this work

Chemistry

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Abstract

Monomeric organolithium (LiR) complexes could provide enhanced Li–C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CH₂SiMe₃)(κ³-N,N′,N′′-Me⁶Tren)] (1), where Me⁶Tren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes via ligand C–H and C–N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal C[double bond, length as m-dash]O insertion and C–H activation reaction patterns.

Original language	English
Pages (from-to)	10707-10713
Number of pages	7
Journal	Dalton Transactions
Volume	51
Issue number	28
Early online date	26 Nov 2021
DOIs	https://doi.org/10.1039/D1DT03532K
Publication status	Published - 28 Jul 2022

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title = "A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies",

abstract = "Monomeric organolithium (LiR) complexes could provide enhanced Li–C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CH2SiMe3)(κ3-N,N′,N′′-Me6Tren)] (1), where Me6Tren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes via ligand C–H and C–N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal C[double bond, length as m-dash]O insertion and C–H activation reaction patterns. ",

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doi = "10.1039/D1DT03532K",

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T1 - A monomeric (trimethylsilyl)methyl lithium complex

T2 - synthesis, structure, decomposition and preliminary reactivity studies

AU - Davison, Nathan

AU - Waddell, Paul G.

AU - Casey, Dixon

AU - Wills, Corinne

AU - Penfold, Thomas J.

AU - Lu, Erli

PY - 2022/7/28

Y1 - 2022/7/28

N2 - Monomeric organolithium (LiR) complexes could provide enhanced Li–C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CH2SiMe3)(κ3-N,N′,N′′-Me6Tren)] (1), where Me6Tren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes via ligand C–H and C–N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal C[double bond, length as m-dash]O insertion and C–H activation reaction patterns.

AB - Monomeric organolithium (LiR) complexes could provide enhanced Li–C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CH2SiMe3)(κ3-N,N′,N′′-Me6Tren)] (1), where Me6Tren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes via ligand C–H and C–N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal C[double bond, length as m-dash]O insertion and C–H activation reaction patterns.

U2 - 10.1039/D1DT03532K

DO - 10.1039/D1DT03532K

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 28

ER -

A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies

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