TY - JOUR
T1 - M(C6H6R)2 (R = BH, Be; M = Cr, Mo, W)
T2 - Transition-metal sandwich complexes with η7-coordination borepin and beryllepin: A DFT study
AU - Tang, Yupeng
AU - Zhao, Yanfei
AU - Wang, Gaofeng
AU - Li, Nan
N1 - Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2019/10/1
Y1 - 2019/10/1
N2 - In this article, the geometrical and electronic structures of a series of borepin and beryllepin transition-metal sandwich complexes M(C6H6R)2 (R = BH, Be; M = Cr, Mo, W) have been systematically investigated at the B3LYP and BP86 levels of theory. Comparing to Cr(C6H6)2, the optimized structures possess the relatively larger binding energies, similar HOMO-LUMO and fundamental gaps. The topology parameters and energy decomposition analyses show the M-C6H6R bonding interactions are mostly covalent bonds. The detailed molecular orbital and Adaptive Natural Density Partitioning analyses indicate that the spd-π interaction plays an important role in stabilizing M(C6H6R)2. Nucleus independent chemical shift (NICS) analysis indicates the aromaticity of the C6H7B/C6H6Be ligands is strengthened by the metal atoms in the sandwich complexes M(C6H6R)2. Based on the negative free energy changes of the reactions of the C6H7B/C6H6Be ligands with M(C6H6)2, the concerned borepin and beryllepin sandwich complexes probably are synthesized in gas phases.
AB - In this article, the geometrical and electronic structures of a series of borepin and beryllepin transition-metal sandwich complexes M(C6H6R)2 (R = BH, Be; M = Cr, Mo, W) have been systematically investigated at the B3LYP and BP86 levels of theory. Comparing to Cr(C6H6)2, the optimized structures possess the relatively larger binding energies, similar HOMO-LUMO and fundamental gaps. The topology parameters and energy decomposition analyses show the M-C6H6R bonding interactions are mostly covalent bonds. The detailed molecular orbital and Adaptive Natural Density Partitioning analyses indicate that the spd-π interaction plays an important role in stabilizing M(C6H6R)2. Nucleus independent chemical shift (NICS) analysis indicates the aromaticity of the C6H7B/C6H6Be ligands is strengthened by the metal atoms in the sandwich complexes M(C6H6R)2. Based on the negative free energy changes of the reactions of the C6H7B/C6H6Be ligands with M(C6H6)2, the concerned borepin and beryllepin sandwich complexes probably are synthesized in gas phases.
KW - Beryllepin
KW - Borepin
KW - Energy decomposition analysis
KW - Nucleus independent chemical shift
KW - Sandwich compound
UR - https://www.scopus.com/pages/publications/85071457496
U2 - 10.1016/j.comptc.2019.112562
DO - 10.1016/j.comptc.2019.112562
M3 - Article
AN - SCOPUS:85071457496
SN - 2210-271X
VL - 1165
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
M1 - 112562
ER -