Abstract
Elementary reaction mechanisms constitute a fundamental infrastructure for chemical processes as a whole. However, while these mechanisms are well understood for second-period elements, involving those of the third period and beyond can introduce unorthodox reactivity. Combining crossed molecular beam experiments with electronic structure calculations and molecular dynamics simulations, we provide compelling evidence on an exotic insertion of an unsaturated sigma doublet radical into a silicon-hydrogen bond as observed in the barrierless gas-phase reaction of the D1-ethynyl radical (C(2)D) with silane (SiH(4)). This pathway, which leads to the D1-silylacetylene (SiH(3)CCD) product via atomic hydrogen loss, challenges the prerequisite and fundamental concept that two reactive electrons and an empty orbital are required for the open shell, unsaturated radical reactant to insert into a single bond.