TY - JOUR
T1 - Carbones as Ligands in Novel Main-Group Compounds E[C(NHC)2]2 (E=Be, B+, C2+, N3+, Mg, Al+, Si2+, P3+)
T2 - A Theoretical Study
AU - Hermann, Markus
AU - Frenking, Gernot
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/3/8
Y1 - 2017/3/8
N2 - Quantum chemical calculations of the main-group compounds E[C(NHCMe)2]2 (E=Be, B+, C2+, N3+, Mg, Al+, Si2+, P3+) have been carried out using density functional theory at the BP86/def2-TZVPP and BP86-D3(BJ)/def2-TZVPP levels of theory. The geometry optimization at BP86/def2-TZVPP gives equilibrium structures with two-coordinated species E and bending angles C-E-C between 152.5° (E=Be) and 110.5° (E=Al). Inclusion of dispersion forces at BP86-D3(BJ)/def2-TZVPP yields a three-coordinated beryllium compound Be[C(NHCMe)2]2 as the only energy minimum form. Three-coordinated isomers are found besides the two-coordinated energy minima for the boron and carbon cations B[C(NHCMe)2]2+ and C[C(NHCMe)2]22+. The three-coordinated form of the boron compound is energetically lower lying than the two-coordinated form, while the opposite trend is calculated for the carbon species. The theoretically predicted bond dissociation energies suggest that all compounds are viable species for experimental studies. The X-ray structure of the benzoannelated homologue of P[C(NHCMe)2]23+ that was recently reported by Dordevic et al. agrees quite well with the calculated geometry of the molecule. A detailed bonding analysis using charge and energy decomposition methods shows that the two-coordinated neutral compounds Be[C(NHCMe)2]2 and Mg[C(NHCMe)2]2 possess strongly positively charged atoms Be and Mg. The carbodicarbene groups C(NHCMe)2 serve as acceptor ligands in the compounds and may be sketched with dative bonds (NHCMe)2C←E→C(NHCMe)2 (E=Be, Mg). Dative bonds in which the carbones C(NHCMe)2 are donor ligands are suggested for the cations (NHCMe)2C→E←C(NHCMe)2 (E=B+, Al+). The dications and trications possess electron-sharing bonds in which the bonding situation is best described with the formula [(NHCMe)2C]+-E-[C(NHCMe)2]+ (E=C, Si, N+, P+).
AB - Quantum chemical calculations of the main-group compounds E[C(NHCMe)2]2 (E=Be, B+, C2+, N3+, Mg, Al+, Si2+, P3+) have been carried out using density functional theory at the BP86/def2-TZVPP and BP86-D3(BJ)/def2-TZVPP levels of theory. The geometry optimization at BP86/def2-TZVPP gives equilibrium structures with two-coordinated species E and bending angles C-E-C between 152.5° (E=Be) and 110.5° (E=Al). Inclusion of dispersion forces at BP86-D3(BJ)/def2-TZVPP yields a three-coordinated beryllium compound Be[C(NHCMe)2]2 as the only energy minimum form. Three-coordinated isomers are found besides the two-coordinated energy minima for the boron and carbon cations B[C(NHCMe)2]2+ and C[C(NHCMe)2]22+. The three-coordinated form of the boron compound is energetically lower lying than the two-coordinated form, while the opposite trend is calculated for the carbon species. The theoretically predicted bond dissociation energies suggest that all compounds are viable species for experimental studies. The X-ray structure of the benzoannelated homologue of P[C(NHCMe)2]23+ that was recently reported by Dordevic et al. agrees quite well with the calculated geometry of the molecule. A detailed bonding analysis using charge and energy decomposition methods shows that the two-coordinated neutral compounds Be[C(NHCMe)2]2 and Mg[C(NHCMe)2]2 possess strongly positively charged atoms Be and Mg. The carbodicarbene groups C(NHCMe)2 serve as acceptor ligands in the compounds and may be sketched with dative bonds (NHCMe)2C←E→C(NHCMe)2 (E=Be, Mg). Dative bonds in which the carbones C(NHCMe)2 are donor ligands are suggested for the cations (NHCMe)2C→E←C(NHCMe)2 (E=B+, Al+). The dications and trications possess electron-sharing bonds in which the bonding situation is best described with the formula [(NHCMe)2C]+-E-[C(NHCMe)2]+ (E=C, Si, N+, P+).
KW - bonding analysis
KW - carbodicarbene
KW - carbones
KW - dative bonding
KW - electron-shared bonding
KW - main-group complexes
KW - quantum chemical calculations
UR - http://www.scopus.com/inward/record.url?scp=85027953836&partnerID=8YFLogxK
U2 - 10.1002/chem.201604801
DO - 10.1002/chem.201604801
M3 - 文章
C2 - 28004870
AN - SCOPUS:85027953836
SN - 0947-6539
VL - 23
SP - 3347
EP - 3356
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 14
ER -