Density functional investigation of reaction of borohydride cation BH2+ with propylene.

Abstract

The reactions of BH2+ with propylene (CH2=CHCH3) to form both the adducts BC3H8+ and the H2-elimination products BC3H6+ + H2 have been investigated at the density functional B3LYP/6-311G(d,p) level of theory. It is shown that the electrophilic attacks of BH2+ towards two olefinic carbons of H2C=CHCH3 and two subsequent 1,3-H-shifts may form four low-lying BC3H8+ isomers (with the relative energies in parentheses in kcal/mol): 1 BH2+.CH2CHCH3 (0.0), 1' BH2+.CH3CHCH2 (6.3), 3 BHCH2CH2CH3+ (4.3), and 4 BHCH(CH3)2+ (5.0), respectively. On the other hand, further H2-eliminations may also occur easily between B-C bonds of isomers 1 and 1' and between C-C bonds of isomers 3 and 4 to form two dissociation products (P1) HBCHCHCH3+ + H2 and (P2) HBC(CH3)CH2+ + H2, with H2-elimination from isomer 1 to be energetically most favorable. According to our calculated mechanism, the collisional stabilization processes of low-lying isomers 1, 1', 3, and 4 may compete extensively with their H2-eliminations processes for the title reaction, leading mainly to some linear carborane cations. This study may be helpful for understanding the stereochemical aspects of borohydride cations towards alkylenes.