Premium Inductive effects in radicals calculated from DFT energies; substituted bicyclo[2.2.2]octan‐1‐yloxy radicalsPremium
journal of computational chemistry
Abstract Energies of a series of 4‐substituted 1‐oxybicyclo[2.2.2]octan‐1‐yloxy radicals with 18 various substituents were calculated within the framework of the DFT theory at the levels UB3LYP/6‐311+G(d,p)//UB3LYP/6‐311+G(d,p) and UB3LYP/6‐311++G(2df,p)//UB3LYP/6‐311+G(d,p) and compared with similar series of the parent alcohols, their deprotonated and protonated forms calculated at the levels B3LYP/6‐311+G(d,p)//B3LYP/6‐311+G(d,p) and B3LYP/6‐311++G(2df,p)//B3LYP/6‐311+G(d,p). The two levels are of the same performance and both are sufficient for molecules of this type according to comparison with scarce experimental gas‐phase acidities and basicities. The substituent effects were analyzed in terms of isodesmic equations. In addition to strong dependence on the substituent inductive effect, a slight dependence on the electronegativity of the first atom of the substituent was proven in certain cases. In all aspects, there is no qualitative difference between the effects on radicals and on similar closed shell species. Radicals behave as slightly electron deficient; the substituent effect is weaker than that on the ions but stronger than on neutral molecules. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007.
Subject(s)chemistry , computational chemistry , crystallography , density functional theory , deprotonation , electronegativity , inductive effect , ion , isodesmic reaction , medicinal chemistry , molecule , organic chemistry , protonation , radical , stereochemistry , substituent
SCImago Journal Rank0.907
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