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Updated: Jul 1, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Synthesis and Reactivity of the [NCCCO]- Cyanoketenate Anion
Tongtong Wang1, Zhuangzhuang Guo1, Laura E English2
1School of Chemical Science and Engineering, Tongji University, 1239 Siping Rd, Shanghai, China, 200092.
Abstract:
Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds. We report the first synthesis of the cyanoketenate anion in [K(18-crown-6)][NCCCO] (1) as a stable molecule on a multigram scale in excellent yields (>90 %). The structure of this molecule is probed crystallographically and computationally. We also explore the protonation of 1, and its reaction with triphenylsilylchloride and carbon dioxide. In all cases, anionic dimers are formed. The cyanoketene could be synthesized and crystallographically characterized when stabilized by a N-heterocyclic carbene. The cyanoketenate is a very useful unsaturated building block containing N, C and O atoms that can now be explored with relative ease and will undoubtedly unlock more interesting reactivity.
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