A crossed molecular beams and computational study on the unusual reactivity of banana bonds of cyclopropane (c-C3H6; ) through insertion by ground state carbon atoms (C(3Pj))

Abstract

The mechanism and chemical dynamics of the reaction of ground electronic state atomic carbon C(³P_j) with cyclopropane c-C₃H₆ have been explored by combining crossed molecular beams experiments with electronic structure calculations of the pertinent triplet C₄H₆ potential energy surface and statistical computations of product branching ratios under single-collision conditions. The experimental findings suggest that the reaction proceeds via indirect scattering dynamics through triplet C₄H₆ reaction intermediate(s) leading to C₄H₅ product(s) plus atomic hydrogen via a tight exit transition state, with the overall reaction exoergicity evaluated as 231 ± 52 kJ mol⁻¹. The calculations indicate that C(³P_j) can easily insert into one of the three equivalent C–C ‘banana’ bonds of cyclopropane overcoming a low barrier of only 2 kJ mol⁻¹ following the formation of a van der Waals reactant complex stabilized by 15 kJ mol⁻¹. The carbon atom insertion into one of the six C–H bonds is also feasible via a slightly higher barrier of 5 kJ mol⁻¹. These results highlight an unusual reactivity of cyclopropane's banana C–C bonds, which behave more like unsaturated C–C bonds with a π-character than saturated σ C–C bonds, which are known to be generally unreactive toward the ground electronic state atomic carbon such as in ethane (C₂H₆). The statistical theory predicts the overall product branching ratios at the experimental collision energy as 50% for 1-butyn-4-yl, 33% for 1,3-butadien-2-yl, i-C₄H₅, and 11% for 1,3-butadien-1-yl, n-C₄H₅, with i-C₄H₅ (230 kJ mol⁻¹ below the reactants) favored by the C–C insertion providing the best match with the experimentally observed reaction exoergicity. The C(³P_j) + c-C₃H₆ reaction is predicted to be a source of C₄H₅ radicals under the conditions where its low entrance barriers can be overcome, such as in planetary atmospheres or in circumstellar envelopes but not in cold molecular clouds. Both i- and n-C₄H₅ can further react with acetylene eventually producing the first aromatic ring and hence, the reaction of the atomic carbon with c-C₃H₆ can be considered as an initial step toward the formation of benzene.