A Computational Understanding of Solvent Effect on the Structure, Electronic, Thermochemical, and Spectroscopic Properties of Ni(η²-C₆H₄)(H₂PCH₂CH₂PH₂) Complex

Abstract

Here we report the density functional calculations of the molecular parameters including the energy, geometries, electric dipole moments, vibrational IR frequencies, and 1H and 13C NMR chemical shifts of Ni(η2‐C6H4)(H2PCH2CH2PH2) (a benzyne complex). Based on the polarizable continuum model (PCM), the effect of polarity of the solvent on these parameters was explored. The wavenumbers of υ(C1–C2) as well as the 1H and 13C NMR chemical shift values of complex in various solvents were calculated and correlated with the Kirkwood–Bauer–Magat equation (KBM), the solvent acceptor numbers (ANs), and the linear solvation energy relationship (LSER). The bonding interaction between the benzyne and Ni(H2PCH2CH2PH2) fragment was analyzed by means of the energy decomposition analysis (EDA). The character of the Ni–C bonds of the molecules was analyzed by natural bond orbital (NBO) analysis. Also, Monte Carlo simulations were used for the calculation of the total energy and solvation free energy of the complex in water.