Semiempirical Treatment of Hindered Rotation in Simple Hydrides and Halosubstituted Ethanelike Molecules

摘要

A semiempirical electrostatic model for internal rotation in certain molecules is developed from the integral Hellmannmdash;Feynman theorem. The model is shown to be capable of rationalizing and predicting barriers to internal rotation in terms of wellhyphen;established physical and chemical concepts. For simple hydrides containing only atoms from the first two rows of the periodic table (CH3NH2, CH3SH, etc.), the barriers to methyl rotation are shown to be correlated with the electronegativity of the heavy atom (N,S, etc.). Effects due todandfcharacter in bond hybrids appear to be important only for molecules containing atoms in Rows III and IV of the periodic table. The remarkably low internalhyphen;rotation barriers for acetylene derivatives are attributed to the polarizability of the triple bond. The model is consistent with observed changes of the barrier with fluorosubstitution in ethane and methyl silane when inductive effects are included. The sets CH3CH2X and CF3CH2X are examined, and barriers are predicted for SiH3CH2X molecules giving 1.99, 2.44, 2.45, and 2.32 kcal/mole for X=F, Cl, Br, I, respectively. Barriers are also predicted for SiH3CHF2(2.00), SiH3CF3(2.42), SiH3SiHF2(0.85), and SiH3SiF3(0.81). It is argued that disilane should have a barrier of 1.08 kcal/molemdash;lower than the barriers for ethane or digermane. The relationship between the shape and the physical source of the barrier is discussed. The model predictsV6ap;minus;0.005V3for molecules of the type considered. For ethyl fluoride,V6is predicted to be minus;16 cal/mole compared to the experimental value of minus;15 cal/mole. The relations between this model and other theories of the barrier are briefly discussed.