Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon-Piperidine.

ABSTRACT: Recent quantum chemical computations demonstrated the electron-acceptance behavior of this highly reactive cyclo[18]carbon (C₁₈) ring with piperidine (pip). The C₁₈-pip complexation exhibited a double-well potential along the N-C reaction coordinate, forming a van der Waals (vdW) adduct and a more stable, strong covalent/dative bond (DB) complex by overcoming a low activation barrier. By means of direct dynamical computations using canonical variational transition state theory (CVT), including the small-curvature tunneling (SCT), we show the conspicuous role of heavy atom quantum mechanical tunneling (QMT) in the transformation of vdW to DB complex in the solvent phase near absolute zero. Below 50 K, the reaction is entirely driven by QMT, while at 30 K, the QMT rate is too rapid (k_T ∼ 0.02 s^-1), corresponding to a half-life time of 38 s, indicating that the vdW adduct will have a fleeting existence. We also explored the QMT rates of other cyclo[n]carbon-pip systems. This study sheds light on the decisive role of QMT in the covalent/DB formation of the C₁₈-pip complex at cryogenic temperatures.

SUBMITTER: Nandi A 

PROVIDER: S-EPMC8900127 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature