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A Computational Understanding of Solvent Effect on the Structure, Electronic, Thermochemical, and Spectroscopic Properties of Ni(η 2 ‐ C 6 H 4 )( H 2 PCH 2 CH 2 PH 2 ) Complex
Author(s) -
Shabani Mozhdeh,
Ghiasi Reza,
Yousefi Mohammad,
Ketabi Sepideh
Publication year - 2017
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201700071
Subject(s) - chemistry , solvation , natural bond orbital , polarizable continuum model , computational chemistry , carbon 13 nmr , solvent effects , polarizability , chemical shift , molecule , density functional theory , dipole , solvent , stereochemistry , organic chemistry
Here we report the density functional calculations of the molecular parameters including the energy, geometries, electric dipole moments, vibrational IR frequencies, and 1 H and 13 C NMR chemical shifts of Ni(η 2 ‐ C 6 H 4 )( H 2 PCH 2 CH 2 PH 2 ) (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 1 H and 13 C 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( H 2 PCH 2 CH 2 PH 2 ) 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.