Solvent effect on isomerization reaction of [(eta(5)-C5H5)(CO)(2)Re=C (C2HB10H10)(C6H5)] carbene complex to [(eta(5)-C5H5)(CO)(COC2HB10H10) Re CC6H5] carbyne complex: A computational investigation

摘要

In this study, solvent effect on isomerization reaction of [(eta(5)-C5H5)(CO)(2)Re=C(C2HB10H10)(C6H5)] carbene complex to [(eta(5)-C5H5)(CO)(COC2HB10H10)Re CC6H5] carbyne complex was investigated using MPW1PW91-bases quantum mechanical calculations. Solvent effect was explored through applying polarizable continuum model (PCM), which is a self-consistent reaction field (SCRF) approach. The reaction was explored in bromoethan, cycloHexanone, n,n-dinethylformamide (DMF), o-nitrotoluene, and tetraHydroThiophene-s,s-dioxid (THTDO). Influence of dielectric constant values of these solvents on the relative energies, thermodynamics parameters, and frontier orbitals of the complexes was revealed. Furthermore, percentage compositions of two isomers were inspected, in terms of the defined groups of frontier orbitals, to evaluate characters of their M-C-carbene and M-C-carbyne bonds. Rate constant of the isomerization reaction was calculated from 200 K to1200 K in gas phase. (C) 2018 Elsevier B.V. All rights reserved.