C鈥揌路路路蟺 Interactions and the Nature of the Donor Carbon Atom

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• 作者：Brijesh Kumar Mishra ; Milind Madhusudan Deshmukh ; Ramanathan Venkatnarayan
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：September 19, 2014
• 年：2014
• 卷：79
• 期：18
• 页码：8599-8606
• 全文大小：419K
• ISSN：1520-6904

文摘

The influence of multiple substituents (F, CH₃, NO₂, CN, Cl, OH and NH₂) on the C鈥揌路路路蟺 interaction in benzene鈥揺thylene complex was investigated using the estimated CCSD(T) method and complete basis set limit. The results were compared with our earlier reported complexes of benzene鈥揳cetylene and benzene鈥搈ethane, thus completing the sp, sp² and sp³ series of C鈥揌 donors. The stabilization energy values for multiple fluoro-substituted benzene鈥揺thylene complexes are found to be very close to those of the multiple fluoro-substituted benzene鈥搈ethane complexes. Expectedly, the stabilization energies for the multiple methyl-substituted benzene鈥揺thylene complexes lie between those of the multiple methyl-substituted benzene鈥搈ethane and benzene鈥揳cetylene complexes. Energy decomposition analysis using the DFT-SAPT method predicts the dispersion energy to be dominant, similar to the benzene鈥搈ethane complexes. For the symmetrically disubstituted complexes (-OH, -Cl, -NH₂, -CN and -NO₂), additional C鈥揌路路路X interaction was observed, possibly due to the angular orientation of the ethylene molecule. Multidimensional correlation analysis between the electrostatic, dispersion and exchange-repulsion with the C鈥揌路路路蟺 interaction distance (r), Hammett constant (蟽) and the molar refractivity (MR) revealed strong correlation between dispersion energy and the C鈥揌路路路蟺 interaction distance (r) as well as molar refractivity (MR).