Abstract
Density functional theory with the B3LYP hybrid functional and 6–31G* basis set was used to study the geometric and electronic structure of H 2 C = CHR (R = H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , and C 5 H 11 ) olefins, their carbocations formed in the addition of the proton to the olefins, R′-S-H aliphatic thiols (R′ = H, CH 3 , C 2 H 5 , and C 3 H 7 ), the products of the addition of thiols to carbocations, and the final products of the addition of thiols to olefins. The proton affinity of the olefins and the products of the addition of thiols to olefins was calculated. The conclusion was drawn that the limiting stage in the nonradical addition of thiols to olefins catalyzed by acids was proton transfer from the protonated reaction product to the olefin. The theoretical results were compared with the experimental data on the electrophilic addition of polymercaptan to heptene-1.