Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? the Silicon (Si(³P))-Dimethylacetylene (C₄H₆(X¹A_1g)) System as a Case Study

The bimolecular gas phase reaction of ground-state silicon (Si; ³P) with dimethylacetylene (C₄H₆; X¹A_1g) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC₄H₄ isomer(s) and molecular hydrogen (H₂) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC₄H₄ isomers (¹p8-¹p24) in overall exoergic reaction(s) (-107-20⁺¹² kJ mol^-1). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si(³P), with a hydrocarbon molecule.