TY - JOUR
T1 - A theoretical approach to substituent effects. Interactions between directly bonded groups in the neutrals X-NH2, X-OH, and X-F and the anions X-NH− and X-O−
AU - Hinde, Alan L.
AU - Pross, Addy
AU - Radom, Leo
PY - 1980/1/1
Y1 - 1980/1/1
N2 - Ab initio molecular orbital calculations have been carried out for the neutrals X-NH2, X-OH, and X-F and the anions X-NH− and X-O− with substituents X = Li, BeH, BH2, CH3, NH2, OH, and F. All structures have been fully optimized with the 4‐31G basis set which is found to perform considerably better than the minimal STO‐3G basis in predicting the lengths of strongly polar bonds. A quantitative analysis of interactions between the directly bonded groups, utilizing energy changes in hydrogenation reactions, is presented and rationalized with the aid of perturbation molecular orbital theory. Favorable interactions occur when electron‐donor groups bond to electron‐acceptor groups. This applies to both σ and π interactions, the relative importance of which depends on the particular substituents.
AB - Ab initio molecular orbital calculations have been carried out for the neutrals X-NH2, X-OH, and X-F and the anions X-NH− and X-O− with substituents X = Li, BeH, BH2, CH3, NH2, OH, and F. All structures have been fully optimized with the 4‐31G basis set which is found to perform considerably better than the minimal STO‐3G basis in predicting the lengths of strongly polar bonds. A quantitative analysis of interactions between the directly bonded groups, utilizing energy changes in hydrogenation reactions, is presented and rationalized with the aid of perturbation molecular orbital theory. Favorable interactions occur when electron‐donor groups bond to electron‐acceptor groups. This applies to both σ and π interactions, the relative importance of which depends on the particular substituents.
UR - http://www.scopus.com/inward/record.url?scp=84986513613&partnerID=8YFLogxK
U2 - 10.1002/jcc.540010203
DO - 10.1002/jcc.540010203
M3 - Article
AN - SCOPUS:84986513613
SN - 0192-8651
VL - 1
SP - 118
EP - 128
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
IS - 2
ER -