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 - Funding Information:
C. J., L. M. and N. C. thank the Australian Research Council for funding. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386‐21‐1‐4048. L. M. is a senior member of the Institut Universtaire de France and thanks the Alexander von Humboldt Foundation. L. F. L. acknowledges the support of an Australian Government Research Training Program (RTP) International Scholarship. Part of this research was undertaken on the MX1 beam line at the Australian Synchrotron, Victoria, Australia. Open Access publishing facilitated by Monash University, as part of the Wiley ‐ Monash University agreement via the Council of Australian University Librarians.
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 - https://www.scopus.com/pages/publications/85183401740
U2 - 10.1002/chem.202303949
DO - 10.1002/chem.202303949
M3 - Article
AN - SCOPUS:85183401740
SN - 1521-3765
VL - 30
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 15
M1 - e202303949
ER -