{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,6]],"date-time":"2026-03-06T23:04:35Z","timestamp":1772838275891,"version":"3.50.1"},"reference-count":23,"publisher":"Wiley","issue":"63","license":[{"start":{"date-parts":[[2024,10,26]],"date-time":"2024-10-26T00:00:00Z","timestamp":1729900800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2024,11,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Carbyne free radicals \n<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem202402592-gra-0061.png\" xlink:title=\"image\"\/> (RC) are usually associated with high\u2010energy processes, thus research on their preparation, chemical reactivity, and prevalence under mild conditions is scarce. Recently, it was reported that metallo\u2010complexes containing CR ligands may undergo spontaneous degradation in aqueous solutions to produce free RC radicals. These highly reactive species may react with each other to form the corresponding alkyne and other products. The reaction of 1,1,1 halo\u2010carbo\u2010hydrates with Cr(II) ions also forms RC radicals under mild conditions. Herein, we report two additional synthetic routes that produce free RC radicals under mild conditions. First, the reaction between metallic zinc and acetic anhydride produces 2\u2010butyne and several other C<jats:sub>2<\/jats:sub>, C<jats:sub>3<\/jats:sub>, and C<jats:sub>4<\/jats:sub> compounds. Isotopic\u2010labeling experiments indicate that the formation of 2\u2010butyne results from an inter\u2010molecular reaction in which two RC moieties from two acetic anhydride molecules combine in solution. In addition, the degradation of the tri\u2010molybdenum complex [Mo<jats:sub>3<\/jats:sub>(H<jats:sub>3<\/jats:sub>CC\u2261CCH<jats:sub>3<\/jats:sub>)(OAc)(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>Br<jats:sub>7<\/jats:sub>], in which a 2\u2010butyne ligand is coordinated to the Mo<jats:sub>3<\/jats:sub> framework in a \u03bc<jats:sub>3<\/jats:sub>\u2010\u03b7<jats:sub>2<\/jats:sub> (\u22a5) binding mode in aqueous solution produces several C<jats:sub>2<\/jats:sub>, C<jats:sub>3<\/jats:sub>, C<jats:sub>4<\/jats:sub> and C<jats:sub>5<\/jats:sub> molecules. This indicates the formation of free CH<jats:sub>3<\/jats:sub>C radicals by a homolytic cleavage of the carbon\u2010carbon triple bond.<\/jats:p>","DOI":"10.1002\/chem.202402592","type":"journal-article","created":{"date-parts":[[2024,9,4]],"date-time":"2024-09-04T06:54:13Z","timestamp":1725432853000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Novel Methods for the Formation of Free Carbyne Radicals in Solution"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9376-0989","authenticated-orcid":false,"given":"Shay","family":"Avisar","sequence":"first","affiliation":[{"name":"Institute of Chemistry The Hebrew University of Jerusalem Edmond J. Safra Campus, Givat Ram  9190401 Jerusalem Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yahel","family":"Shner","sequence":"additional","affiliation":[{"name":"Institute of Chemistry The Hebrew University of Jerusalem Edmond J. Safra Campus, Givat Ram  9190401 Jerusalem Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Etoile","family":"Cherki","sequence":"additional","affiliation":[{"name":"Institute of Chemistry The Hebrew University of Jerusalem Edmond J. Safra Campus, Givat Ram  9190401 Jerusalem Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Benny","family":"Bogoslavsky","sequence":"additional","affiliation":[{"name":"Institute of Chemistry The Hebrew University of Jerusalem Edmond J. Safra Campus, Givat Ram  9190401 Jerusalem Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5491-5332","authenticated-orcid":false,"given":"Avi","family":"Bino","sequence":"additional","affiliation":[{"name":"Institute of Chemistry The Hebrew University of Jerusalem Edmond J. Safra Campus, Givat Ram  9190401 Jerusalem Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,10,26]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"crossref","unstructured":"D.\u2005F. Forbes Carbon-Centered Free Radicals and Radical Cations: Structure Reactivity and Dynamics Wiley 2010.","DOI":"10.1002\/9780470584118"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00825a007"},{"key":"e_1_2_7_3_1","doi-asserted-by":"crossref","unstructured":"R. Suzuki T. Ando F. Deufel K. Ohmatsu T. Ooi O.\u2005O. Chemie C. 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