Ethynylhydroxycarbene (H–C≡C–C̈–OH)
| Autor: | André K. Eckhardt, Marcel Ruth, Peter R. Schreiner, Bastian Bernhardt |
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| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 143:3741-3746 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.1c00897 |
| Popis: | The species on the C3H2O potential energy surface have long been known to play a vital role in extraterrestrial chemistry. Here we report on the hitherto uncharacterized isomer ethynylhydroxycarbene (H-C≡C-C-OH, 1) generated by high-vacuum flash pyrolysis of ethynylglyoxylic acid ethyl ester and trapped in solid argon matrices at 3 and 20 K. Upon irradiation at 436 nm trans-1 rearranges to its higher lying cis-conformer. Prolonged irradiation leads to the formation of propynal. When the matrix is kept in the dark, 1 reacts within a half-life of ca. 70 h to propynal in a conformer-specific [1,2]H-tunneling process. Our results are fully consistent with computations at the CCSD(T)/cc-pVTZ and the B3LYP/def2-QZVPP levels of theory. |
| Databáze: | OpenAIRE |
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