Skip to main content
Open Access Publications from the University of California

UC Berkeley

UC Berkeley Previously Published Works bannerUC Berkeley

Crossed Beam Experiments and Computational Studies of Pathways to the Preparation of Singlet Ethynylsilylene (HCCSiH; X1A′): The Silacarbene Counterpart of Triplet Propargylene (HCCCH; X3B)


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; Cs; 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.

Many UC-authored scholarly publications are freely available on this site because of the UC's open access policies. Let us know how this access is important for you.

Main Content
For improved accessibility of PDF content, download the file to your device.
Current View