Cyclobutenylidene: A Multifaceted Two-Coordinate Carbon Species Obtained via Skeletal Editing of a Cyclopropenylidene.

CH isomers not only serve as a basis to understand the chemical properties of hydrocarbons but are possible intermediates in combustion and organic reactions in outer space. Cyclobutenylidene (CBY), an elusive CH isomer, is often proposed as a key intermediate in transition-metal-catalyzed metathesis and cycloaddition reactions between carbon-carbon multiple bonds. The geometrical structure of cyclobutenylidene predicted by calculations had been debated as whether it should be regarded as a carbocyclic carbene or a strained bridgehead alkene. Here, we report the synthesis of a crystalline cyclobutenylidene derivative, namely, a 3-silacyclobut-2-en-4-ylidene (SiCBY) via "carbene-to-carbene ring-expansion" reaction of an isolable diaminocyclopropenylidene induced by a silicon analogue of a carbene (silylene). The SiCBY exhibits multifaceted electronic properties which are corroborated by its extremely strong electron-donating properties and ambiphilic reactivity toward small gaseous molecules and C-H bonds. This result introduces an exciting strategy as well as a molecular motif to access low-valent carbon species with unusual electronic properties.