CBAl: Planar hexacoordinate boron (phB) in the global minimum structure

• Published in: Physical chemistry chemical physics : PCCP 2022-09, Vol.24 (37), p.22634-22644
• Main Authors: Das, Prasenjit, Patra, Shanti Gopal, Chattaraj, Pratim Kumar
• Format: Article
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp03532d

Herein, we report for the first time the presence of a planar hexacoordinate boron (phB) atom in the global minimum energy structure of a neutral cluster system. The potential energy surface (PES) has been explored for CB 6 Al 0/+/− systems using density functional theory (DFT). The global minima of CB 6 Al ( 1a ) and CB 6 Al + ( 1b ) contain a phB center. However, the global minimum of CB 6 Al − ( 1c ) does not have a phB atom. The CCSD(T)/aug-cc-pVTZ level of theory has been applied to compute the relative energies of the low-lying isomers with respect to the 1a and 1b structures of CB 6 Al and CB 6 Al + systems, respectively. The exploration of the PES of CB 6 0/+/− systems indicates that the global minima do not contain a phB atom. However, the incorporation of an aluminium (Al) atom into the CB 6 moiety produces structures containing a phB center in the CB 6 Al 0/+ systems. Hence, the Al metal has an important role in attaining a planar geometry having a hexacoordinate boron center. The dynamical stability of CB 6 Al ( 1a ) and CB 6 Al + ( 1b ) was confirmed from the atom-centered density matrix propagation (ADMP) simulation over 20 ps of time at temperatures of 300 K and 400 K. The natural charge computations showed that the charges on the phB are almost zero in both systems. The 1a structure has σ/π-dual aromaticity as predicted from the nucleus independent chemical shift (NICS) values and the gauge-including magnetically induced ring current (GIMIC). Density functional theory-based computations predict planar hexacoordinate boron (phB) in global minimum CB 6 Al 0/+ . The systems are kinetically stable and show σ- and π-electronic delocalization.