{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,10]],"date-time":"2026-02-10T16:02:58Z","timestamp":1770739378638,"version":"3.49.0"},"reference-count":85,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2021,8,1]],"date-time":"2021-08-01T00:00:00Z","timestamp":1627776000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["AN 238\/15-2"],"award-info":[{"award-number":["AN 238\/15-2"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2021,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Reaction of CHI<jats:sub>3<\/jats:sub> with six equivalents of CrCl<jats:sub>2<\/jats:sub> in THF at low temperatures affords [Cr<jats:sub>3<\/jats:sub>Cl<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>2<\/jats:sub>\u2010Cl)<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>3<\/jats:sub>\u2010CH)(thf)<jats:sub>6<\/jats:sub>] as the first isolable high\u2010yield Cr<jats:sup>III<\/jats:sup> \u03bc<jats:sub>3<\/jats:sub>\u2010methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali\u2010metal cyclopentadienides generates isostructural half\u2010sandwich chromium(III)\u2010\u03bc<jats:sub>3<\/jats:sub>\u2010methylidynes [Cp<jats:sup>R<\/jats:sup><jats:sub>3<\/jats:sub>Cr<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>2<\/jats:sub>\u2010Cl)<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>3<\/jats:sub>\u2010CH)] (Cp<jats:sup>R<\/jats:sup>=C<jats:sub>5<\/jats:sub>H<jats:sub>5<\/jats:sub>, C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub>, C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>SiMe<jats:sub>3<\/jats:sub>). Side and decomposition products of the Cl\/Cp<jats:sup>R<\/jats:sup> exchange reactions were identified and structurally characterized for [Cr<jats:sub>4<\/jats:sub>(\u03bc<jats:sub>2<\/jats:sub>\u2010Cl)<jats:sub>4<\/jats:sub>(\u03bc<jats:sub>2<\/jats:sub>\u2010I)<jats:sub>2<\/jats:sub>(\u03bc<jats:sub>4<\/jats:sub>\u2010O)(thf)<jats:sub>4<\/jats:sub>] and [(\u03b7<jats:sup>5<\/jats:sup>\u2010C<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>SiMe<jats:sub>3<\/jats:sub>)CrCl(\u03bc<jats:sub>2<\/jats:sub>\u2010Cl)<jats:sub>2<\/jats:sub>Li(thf)<jats:sub>2<\/jats:sub>]. The Cl\/Cp<jats:sup>R<\/jats:sup> exchange drastically changed the ambient\u2010temperature effective magnetic moment <jats:italic>\u03bc<\/jats:italic><jats:sub>eff<\/jats:sub> from 9.30\/9.11\u2005<jats:italic>\u03bc<\/jats:italic><jats:sub>B<\/jats:sub> (solution\/solid) to 3.63\/4.32\u2005<jats:italic>\u03bc<\/jats:italic><jats:sub>B<\/jats:sub> (Cp<jats:sup>R<\/jats:sup>=C<jats:sub>5<\/jats:sub>Me<jats:sub>5<\/jats:sub>). Reactions of [Cr<jats:sub>3<\/jats:sub>Cl<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>2<\/jats:sub>\u2010Cl)<jats:sub>3<\/jats:sub>(\u03bc<jats:sub>3<\/jats:sub>\u2010CH)(thf)<jats:sub>6<\/jats:sub>] with aldehydes and ketones produce intricate mixtures of species through oxy\/methylidyne exchange, which were partially identified as radical recombination products through GC\/MS analysis and <jats:sup>1<\/jats:sup>H\u2005NMR spectroscopy.<\/jats:p>","DOI":"10.1002\/anie.202106608","type":"journal-article","created":{"date-parts":[[2021,7,2]],"date-time":"2021-07-02T12:30:19Z","timestamp":1625229019000},"page":"20049-20054","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Beyond Takai's Olefination Reagent: Persistent Dehalogenation Emerges in a Chromium(III)\u2010\u03bc<sub>3<\/sub>\u2010Methylidyne Complex"],"prefix":"10.1002","volume":"60","author":[{"given":"Simon","family":"Trzmiel","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Eberhard-Karls-Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle 18 72076 T\u00fcbingen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8694-3111","authenticated-orcid":false,"given":"Jan","family":"Langmann","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physik Universit\u00e4t Augsburg  Universit\u00e4tsstr. 1 86159 Augsburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Daniel","family":"Werner","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Eberhard-Karls-Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle 18 72076 T\u00fcbingen 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For the reactions of1with benzophenone and 9-fluorenone the alkylidene exchange products 1 1-diphenyl-ethylene (Figure\u2005S45) and 9-methylene-9H-fluorene (Figure\u2005S50) were found as the only product species identifiable by1H\u2005NMR spectroscopy (Figures\u2005S7 to S10). GC\/MS analysis revealed trace amounts of numerous other compounds in the product solutions among them iodinated olefination products as well as radical recombination products."},{"key":"e_1_2_6_77_1","unstructured":"Deposition Numbers 2084204 2084205 2084206 2084207 2084208 2084209 2084210 2084211 and 2084212contain the supplementary crystallographic data for this paper. 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