{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,19]],"date-time":"2026-09-19T01:17:21Z","timestamp":1789780641747,"version":"4.0.1"},"reference-count":62,"publisher":"Wiley","issue":"46","license":[{"start":{"date-parts":[[2021,10,11]],"date-time":"2021-10-11T00:00:00Z","timestamp":1633910400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100010663","name":"H2020 European Research Council","doi-asserted-by":"publisher","award":["ERC CoG 772299"],"award-info":[{"award-number":["ERC CoG 772299"]}],"id":[{"id":"10.13039\/100010663","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100005156","name":"Alexander von Humboldt-Stiftung","doi-asserted-by":"publisher","award":["research fellowship"],"award-info":[{"award-number":["research fellowship"]}],"id":[{"id":"10.13039\/100005156","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["CRC325"],"award-info":[{"award-number":["CRC325"]}],"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":[[2021,11,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Detailed <jats:sup>31<\/jats:sup>P{<jats:sup>1<\/jats:sup>H} NMR spectroscopic investigations provide deeper insight into the complex, multi\u2010step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P<jats:sub>4<\/jats:sub>). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non\u2010innocent behavior of the commonly employed terminal reductant Et<jats:sub>3<\/jats:sub>N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)<jats:sub>2<\/jats:sub>][PF<jats:sub>6<\/jats:sub>] (dtbbpy=4,4\u2032\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20102,2\u2032\u2010bipyridine) and 3DPAFIPN. Inspired by the observation of PH<jats:sub>3<\/jats:sub> as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P<jats:sub>4<\/jats:sub> arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.<\/jats:p>","DOI":"10.1002\/anie.202110619","type":"journal-article","created":{"date-parts":[[2021,9,2]],"date-time":"2021-09-02T17:11:07Z","timestamp":1630602667000},"page":"24650-24658","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":41,"title":["Photocatalytic Arylation of P<sub>4<\/sub> and PH<sub>3<\/sub>: Reaction Development Through Mechanistic Insight"],"prefix":"10.1002","volume":"60","author":[{"given":"Robin","family":"Rothfelder","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Verena","family":"Streitferdt","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ulrich","family":"Lennert","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jose","family":"Cammarata","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7826-9833","authenticated-orcid":false,"given":"Daniel J.","family":"Scott","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg 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to track the fate of these H atoms through use of PhPD2as a substrate proved to be complicated by rapid H\/D scrambling. For full details see Section 3.7 of the Supporting Information."},{"key":"e_1_2_6_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08933"},{"key":"e_1_2_6_44_1","unstructured":"\u00a0"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jmr.2013.04.011"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201801250"},{"key":"e_1_2_6_46_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201801250"},{"key":"e_1_2_6_47_1","unstructured":"\u00a0"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00077a009"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp030244g"},{"key":"e_1_2_6_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol101146f"},{"key":"e_1_2_6_51_1","unstructured":"Note however that previous screening efforts have highlighted the importance of using a reductant that can also act as a source of H atoms (presumably to facilitate formation of intermediates including PhPH2and Ph2PH) so replacement of Et3N with alternative reductants is a non-trivial task."},{"key":"e_1_2_6_52_1","volume-title":"CRC Handbook of Chemistry and Physics","author":"Rumble J. R.","year":"2021"},{"key":"e_1_2_6_53_1","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","author":"Bettermann G.","year":"2006"},{"key":"e_1_2_6_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c01414"},{"key":"e_1_2_6_55_1","unstructured":"This may be due to more rapid release of PH3by NaPH2 leading to higher PH3partial pressures within the reaction apparatus."},{"key":"e_1_2_6_56_1","unstructured":"Indeed we have previously proposed that P-H alkylation of Ph2PH may proceedviaanalogous radical attack on the P-P bond of intermediately-formed P2Ph4. See also the similar mechanistic steps shown in Scheme\u20052\u2009b."},{"key":"e_1_2_6_57_1","unstructured":"In principle the use of aryl radicals Ar.to facilitate the degradation of P4could also result in formation of Ar2PH and Ar3P as direct products although formation of these higher phosphines is likely to be less favoured on steric grounds. 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