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
N1 - Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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 - http://www.scopus.com/inward/record.url?scp=85183401740&partnerID=8YFLogxK
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 -