జర్నల్ ఆఫ్ థియరిటికల్ & కంప్యూటేషనల్ సైన్స్
అందరికి ప్రవేశం

నైరూప్య

Computational Studies of 1,3-Dipolar [3 + 2]-Cycloaddition Reactions of Fullerene-C60 with Nitrones

Richard Tia, Jacob Amevor and Evans Adei

Solubility of fullerene-C60 improves with functionalization. 1,3-dipolar [3+2]-cycloaddition reactions of fullerene-C60 with substituted nitrones, a versatile method for fullerene functionalization, were investigated at the MO6/6-31G*//PM3 level of theory to elucidate the effect of electron-releasing (-CH3, -CH2CH3, -CH2CH2CH3, C6H5CH2) substituents and electronwithdrawing substituents (-F, -Cl, -Br, -NC, and -NO2) on the energetics of the reaction; the regio- and stereo-selectivity of the mono- and bis-addition of nitrones; and global reactivity descriptors of the molecular systems to rationalize and predict their chemical reactivity and site selectivity. The results show that electron-withdrawing groups on the nitrones increase the activation barrier of the reaction whereas electron-donating groups decrease the activation barriers. However, electron-withdrawing groups on the nitrones result in more stable products compared to the electron-donating groups. It was found that the reactions with electron-donating substituents on the nitrone are normal electron demand reactions, with C60 as the dipolarophile and the substituted nitrones as the dipoles while the reactions with electron-withdrawing substituents on the nitrones are inverse electron demand reactions. The chemical hardness values show greater positive values for adducts with electron-withdrawing substituents on the nitrone and smaller negative values for adducts with electron-donating substituents on the nitrone, confirming the trend that larger activation barriers accompany reactions with electron-withdrawing substituents on the nitrone while electron-donating substituents lower activation barriers. The activation barriers of the second nitrone addition (bisadduct formation) were found to be lower than the barriers for the first nitrone addition (monoadduct formation). Stereo-chemically, syn-bisaddition was found to be thermodynamically and kinetically stable favoured over anti-bisaddition. Electron donating and electron-withdrawing substituents have a marked effect on the energetics of the reaction.