TY - JOUR
T1 - Stabilization of Heterodiatomic SiC Through Ligand Donation
T2 - Theoretical Investigation of SiC(L)2 (L=NHCMe, CAACMe, PMe3)
AU - Andrada, Diego M.
AU - Frenking, Gernot
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/10/1
Y1 - 2015/10/1
N2 - Quantum chemical calculations have been carried out at the BP86/TZ2P+ level for the compounds SiC(L)2 with L=NHCMe, CAACMe, PMe3 (NHC=N-heterocyclic carbene, CAAC=cyclic (alkyl)aminocarbene). The optimized geometries exhibit a trans arrangement of the ligands L at SiC with a planar coordination when L=NHCMe and PMe3, while a twisted conformation is calculated when L=CAACMe. The bending angle L-Si-C is significantly more acute than the angle L-C-Si. Both angles become wider with the trend PMe3MeMe. The latter trend is also found for the bond dissociation energies of the reaction SiC(L)2→SiC+2L, which have absolute values between De=98-163kcalmol-1. Calculations suggest that the compounds SiC(L)2 have a very large first and second proton affinity, which takes place at the central carbon and silicon atoms, respectively. Energy decomposition analyses indicate that the best description of the bonding situation in SiC(L)2 features a cumulenic carbon-carbon bond and a dative carbon-silicon bond L=C=Si←L at the center.
AB - Quantum chemical calculations have been carried out at the BP86/TZ2P+ level for the compounds SiC(L)2 with L=NHCMe, CAACMe, PMe3 (NHC=N-heterocyclic carbene, CAAC=cyclic (alkyl)aminocarbene). The optimized geometries exhibit a trans arrangement of the ligands L at SiC with a planar coordination when L=NHCMe and PMe3, while a twisted conformation is calculated when L=CAACMe. The bending angle L-Si-C is significantly more acute than the angle L-C-Si. Both angles become wider with the trend PMe3MeMe. The latter trend is also found for the bond dissociation energies of the reaction SiC(L)2→SiC+2L, which have absolute values between De=98-163kcalmol-1. Calculations suggest that the compounds SiC(L)2 have a very large first and second proton affinity, which takes place at the central carbon and silicon atoms, respectively. Energy decomposition analyses indicate that the best description of the bonding situation in SiC(L)2 features a cumulenic carbon-carbon bond and a dative carbon-silicon bond L=C=Si←L at the center.
KW - bonding analysis
KW - density functional calculations
KW - donor-acceptor interactions
KW - silacarbon complex
UR - http://www.scopus.com/inward/record.url?scp=84943199479&partnerID=8YFLogxK
U2 - 10.1002/anie.201502450
DO - 10.1002/anie.201502450
M3 - 文章
AN - SCOPUS:84943199479
SN - 1433-7851
VL - 54
SP - 12319
EP - 12324
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 42
ER -