Revisiting a classic carbocation - DFT, coupled-cluster, and <i>ab initio</i> molecular dynamics computations on barbaralyl cation formation and rearrangements.

ABSTRACT: Density functional theory computations were used to model the formation and rearrangement of the barbaralyl cation (C₉H⁺ ₉). Two highly delocalized minima were located for C₉H⁺ ₉, one of C _s symmetry and the other of D _3h symmetry, with the former having lower energy. Quantum chemistry-based NMR predictions affirm that the lower energy structure is the best match with experimental spectra. Partial scrambling was found to proceed through a C ₂ symmetric transition structure associated with a barrier of only 2.3 kcal mol^-1. The full scrambling was found to involve a C _2v symmetric transition structure associated with a 5.0 kcal mol^-1

SUBMITTER: Guo W 

PROVIDER: S-EPMC11385376 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature