Ethynylsilylene (HCCSiH; X¹A') has been prepared in the gas phase through the elementary reaction of singlet dicarbon (C₂) with silane (SiH₄) under single-collision conditions. Electronic structure calculations reveal a barrierless reaction pathway involving 1,1-insertion of dicarbon into one of the silicon-hydrogen bonds followed by hydrogen migration to form the 3-sila-methylacetylene (HCCSiH₃) intermediate. The intermediate undergoes unimolecular decomposition through molecular hydrogen loss to ethynylsilylene (HCCSiH; C_s; X¹A'). The dicarbon-silane system defines a benchmark to explore the consequence of a single collision between the simplest "only carbon" molecule (dicarbon) with the prototype of a closed-shell silicon hydride (silane) yielding a nonclassical silacarbene, whose molecular geometry and electronic structure are quite distinct from the isovalent triplet propargylene (HCCCH; C₂; ³B) carbon-counterpart. These organosilicon transients cannot be prepared through traditional organic, synthetic methods, thus opening up a versatile path to access the previously largely elusive class of silacarbenes.

Fullerenes (C₆₀, C₇₀) detected in planetary nebulae and carbonaceous chondrites have been implicated to play a key role in the astrochemical evolution of the interstellar medium. However, the formation mechanism of even their simplest molecular building block-the corannulene molecule (C₂₀H₁₀)-has remained elusive. Here we demonstrate via a combined molecular beams and ab initio investigation that corannulene can be synthesized in the gas phase through the reactions of 7-fluoranthenyl (C₁₆H₉˙) and benzo[ghi]fluoranthen-5-yl (C₁₈H₉˙) radicals with acetylene (C₂H₂) mimicking conditions in carbon-rich circumstellar envelopes. This reaction sequence reveals a reaction class in which a polycyclic aromatic hydrocarbon (PAH) radical undergoes ring expansion while simultaneously forming an out-of-plane carbon backbone central to 3D nanostructures such as buckybowls and buckyballs. These fundamental reaction mechanisms are critical in facilitating an intimate understanding of the origin and evolution of the molecular universe and, in particular, of carbon in our galaxy.