CB6Al0/+: Planar hexacoordinate boron (phB) in the global minimum structure. Issue 37 (15th September 2022)

• Record Type: Journal Article
• Authors: Das, Prasenjit; Patra, Shanti Gopal; Chattaraj, Pratim Kumar
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 37(2022)
• Page Start: 22634
• Page End: 22644
• Publication Date: 2022-09-15
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp03532d
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Density functional theory-based computations predict planar hexacoordinate boron (phB) in global minimum CB6 Al 0/+ . The systems are kinetically stable and show σ- and π-electronic delocalization. Abstract : 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 CB6 Al 0/+/− systems using density functional theory (DFT). The global minima of CB6 Al (1a ) and CB6 Al + (1b ) contain a phB center. However, the global minimum of CB6 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 CB6 Al and CB6 Al + systems, respectively. The exploration of the PES of CB6 0/+/− systems indicates that the global minima do not contain a phB atom. However, the incorporation of an aluminium (Al) atom into the CB6 moiety produces structures containing a phB center in the CB6 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 CB6 Al (1a ) and CB6 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).