Cyclometalation in the (η3-C5H5)Co(η2-C2H2)(PMe3) and (η3-C9H7) Co(η2-C2H2) (PMe3) complexes: A computational investigation

This research examined the cyclometalation in the (eta(3)-C5H5)Co(eta(2)-C2H2)(PMe3) and (eta(3)-C9H7)Co(eta(2)-C2H2) (PMe3) complexes by using mPW1PW91 functional. Thermodynamic and kinetic parameters of this reaction were computed. The solvent effects were studied by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and reactivity parameters (hardness, chemical potential, electrophilicity). The Hirshfeld population analysis was performed based on optimized structures. The rate constant of the cyclometalation reaction was computed from 300 to 1200 K, in the gas phase. In addition, the synchronicity values of this reaction were determined. Our findings revealed, this reaction was favorable energetically in both gas and solution phases. The larger rate constant values were in the presence of Cp ring than In ring. (C) 2020 Elsevier B.V. All rights reserved.