Publication Date:
2011-06-07
Description:
Formal reduction potentials, E °′, of a series of 12 para -substituted nitrobenzenes (R―C 6 H 4 ―NO 2 , where R═NH(CH 3 ), NH 2 , OCH 3 , CH 3 , H, OCO(CH 3 ), Cl, CF 3 , CO(CH 3 ), CO(H), CN, and NO 2 ) were measured and related to experimental parameters and the calculated descriptors: the lowest unoccupied molecular orbital (LUMO) energy ( E LUMO ), electron affinity (EA), electrophilicity index ( ω ), and relative group electronegativity ( χ R ). Excellent correlation was obtained in the linear relationship between E °′ and both E LUMO ( R 2 〉 0.99) and ω , followed by EA, χ R , experimental δ 1 H nuclear magnetic resonance (NMR), infrared asymmetric NO 2 stretching frequency ( ν as ), and lastly, δ 13 C NMR. Calculated E LUMO was found to provide the most convenient theoretical means for predicting experimental E °′ while, together with ω , also giving the highest degree of accuracy. Copyright © 2011 John Wiley & Sons, Ltd. Formal reduction potentials of a series of para-substituted nitrobenzenes (R–C6H4–NO2, where R = NH(CH3), NH2, OCH3, CH3, H, OCO(CH3), Cl, CF3, CO(CH3), CO(H), CN and NO2) relates to experimental infrared and nuclear magnetic resonance data as well as to calculated descriptors; LUMO energy, electron affinity, electrophilicity index and Mulliken group electronegativity.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
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