Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride

Yixiao Jiang; K. Yuvaraj; Thayalan Rajeshkumar; Li Feng Lim; Nicholas Cox; Laurent Maron; Cameron Jones

doi:10.1002/chem.202303949

Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride

Yixiao Jiang, K. Yuvaraj, Thayalan Rajeshkumar, Li Feng Lim, Nicholas Cox^*, Laurent Maron^*, Cameron Jones^*

^*Corresponding author for this work

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

2 Citations (Scopus)

Abstract

Reaction of the 1,2-disilylenes {(^DipArAm)Si}₂ (^DipArAm=[(NDip)₂CAr]⁻, Dip=2,6-diisopropylphenyl, Ar=4-C₆H₄Bu^t (Ar’) 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, (^DipArAm)SiOCSi{(NDip)₂CAr} (Ar=Ar’ 3 a or Ph 3 b) with N₂O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, (^DipArAm)(O=)SiOSi(=O)(^DipArAm) (Ar=Ar’ 2 a or Ph 2 b). Both compounds have been fully characterized, and the mechanism of formation of one explored using DFT calculations. Reduction of sila-acid anhydride 2 a with a dimagnesium(I) compound, [{(^MesNacnac)Mg}₂] (^MesNacnac=[(MesNCMe)₂CH]⁻, Mes=mesityl), led to the one-electron reduction of the anhydride and formation of a magnesium complex of a sila-acid anhydride radical anion [(^MesNacnac)Mg{(OSi(^DipAr’Am)}₂O] 5. A combination of EPR spectroscopic studies and DFT calculations reveal the unpaired electron to largely reside on one of the amidinate ligands of the complex.

Original language	English
Article number	e202303949
Journal	Chemistry - A European Journal
Volume	30
Issue number	15
DOIs	https://doi.org/10.1002/chem.202303949
Publication status	Published - 12 Mar 2024

Access to Document

10.1002/chem.202303949

Cite this

@article{a174d5194fb3477a9bfe4ec5a9c3232f,

title = "Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride",

abstract = "Reaction of the 1,2-disilylenes \{(DipArAm)Si\}2 (DipArAm=[(NDip)2CAr]−, Dip=2,6-diisopropylphenyl, Ar=4-C6H4But (Ar{\textquoteright}) 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, (DipArAm)SiOCSi\{(NDip)2CAr\} (Ar=Ar{\textquoteright} 3 a or Ph 3 b) with N2O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, (DipArAm)(O=)SiOSi(=O)(DipArAm) (Ar=Ar{\textquoteright} 2 a or Ph 2 b). Both compounds have been fully characterized, and the mechanism of formation of one explored using DFT calculations. Reduction of sila-acid anhydride 2 a with a dimagnesium(I) compound, [\{(MesNacnac)Mg\}2] (MesNacnac=[(MesNCMe)2CH]−, Mes=mesityl), led to the one-electron reduction of the anhydride and formation of a magnesium complex of a sila-acid anhydride radical anion [(MesNacnac)Mg\{(OSi(DipAr{\textquoteright}Am)\}2O] 5. A combination of EPR spectroscopic studies and DFT calculations reveal the unpaired electron to largely reside on one of the amidinate ligands of the complex.",

keywords = "1,2-disilylene, abnormal N-heterocyclic silylene, magnesium (I), radical, sila-acid anhydride",

author = "Yixiao Jiang and K. Yuvaraj and Thayalan Rajeshkumar and \{Feng Lim\}, Li and Nicholas Cox and Laurent Maron and Cameron Jones",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2024",

month = mar,

day = "12",

doi = "10.1002/chem.202303949",

language = "English",

volume = "30",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag GmbH",

number = "15",

}

TY - JOUR

T1 - Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride

AU - Jiang, Yixiao

AU - Yuvaraj, K.

AU - Rajeshkumar, Thayalan

AU - Feng Lim, Li

AU - Cox, Nicholas

AU - Maron, Laurent

AU - Jones, Cameron

PY - 2024/3/12

Y1 - 2024/3/12

N2 - Reaction of the 1,2-disilylenes {(DipArAm)Si}2 (DipArAm=[(NDip)2CAr]−, Dip=2,6-diisopropylphenyl, Ar=4-C6H4But (Ar’) 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, (DipArAm)SiOCSi{(NDip)2CAr} (Ar=Ar’ 3 a or Ph 3 b) with N2O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, (DipArAm)(O=)SiOSi(=O)(DipArAm) (Ar=Ar’ 2 a or Ph 2 b). Both compounds have been fully characterized, and the mechanism of formation of one explored using DFT calculations. Reduction of sila-acid anhydride 2 a with a dimagnesium(I) compound, [{(MesNacnac)Mg}2] (MesNacnac=[(MesNCMe)2CH]−, Mes=mesityl), led to the one-electron reduction of the anhydride and formation of a magnesium complex of a sila-acid anhydride radical anion [(MesNacnac)Mg{(OSi(DipAr’Am)}2O] 5. A combination of EPR spectroscopic studies and DFT calculations reveal the unpaired electron to largely reside on one of the amidinate ligands of the complex.

AB - Reaction of the 1,2-disilylenes {(DipArAm)Si}2 (DipArAm=[(NDip)2CAr]−, Dip=2,6-diisopropylphenyl, Ar=4-C6H4But (Ar’) 1 a or Ph 1 b) and two abnormal N-heterocyclic silylenes, (DipArAm)SiOCSi{(NDip)2CAr} (Ar=Ar’ 3 a or Ph 3 b) with N2O led to formation of unprecedented examples of uncoordinated silicon analogues of carboxylic acid anhydrides, (DipArAm)(O=)SiOSi(=O)(DipArAm) (Ar=Ar’ 2 a or Ph 2 b). Both compounds have been fully characterized, and the mechanism of formation of one explored using DFT calculations. Reduction of sila-acid anhydride 2 a with a dimagnesium(I) compound, [{(MesNacnac)Mg}2] (MesNacnac=[(MesNCMe)2CH]−, Mes=mesityl), led to the one-electron reduction of the anhydride and formation of a magnesium complex of a sila-acid anhydride radical anion [(MesNacnac)Mg{(OSi(DipAr’Am)}2O] 5. A combination of EPR spectroscopic studies and DFT calculations reveal the unpaired electron to largely reside on one of the amidinate ligands of the complex.

KW - 1,2-disilylene

KW - abnormal N-heterocyclic silylene

KW - magnesium (I)

KW - radical

KW - sila-acid anhydride

UR - https://www.scopus.com/pages/publications/85183401740

U2 - 10.1002/chem.202303949

DO - 10.1002/chem.202303949

M3 - Article

SN - 0947-6539

VL - 30

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

M1 - e202303949

ER -

Stabilization and One Electron Reduction of a Silicon Analogue of a Carboxylic Acid Anhydride

Abstract

Access to Document

Other files and links

Fingerprint

Cite this