{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T14:00:59Z","timestamp":1790258459090,"version":"4.1.0"},"reference-count":76,"publisher":"Wiley","issue":"71","license":[{"start":{"date-parts":[[2020,11,23]],"date-time":"2020-11-23T00:00:00Z","timestamp":1606089600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["Sche 384\/36-1"],"award-info":[{"award-number":["Sche 384\/36-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2020,12,18]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The reaction of [Cp\u2032\u2032\u2032Ni(\u03b7<jats:sup>3<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>)] (<jats:bold>1<\/jats:bold>) with in situ generated phosphenium ions [RR\u2032P]<jats:sup>+<\/jats:sup> yields the unprecedented polyphosphorus cations of the type [Cp\u2032\u2032\u2032Ni(\u03b7<jats:sup>3<\/jats:sup>\u2010P<jats:sub>4<\/jats:sub>R<jats:sub>2<\/jats:sub>)][X] (R=Ph (<jats:bold>2\u2009a<\/jats:bold>), Mes (<jats:bold>2\u2009b<\/jats:bold>), Cy (<jats:bold>2\u2009c<\/jats:bold>), 2,2\u2032\u2010biphen (<jats:bold>2\u2009d<\/jats:bold>), Me (<jats:bold>2\u2009e<\/jats:bold>); [X]<jats:sup>\u2212<\/jats:sup>=[OTf]<jats:sup>\u2212<\/jats:sup>, [SbF<jats:sub>6<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>, [GaCl<jats:sub>4<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>, [BAr<jats:sup>F<\/jats:sup>]<jats:sup>\u2212<\/jats:sup>, [TEF]<jats:sup>\u2212<\/jats:sup>) and [Cp\u2032\u2032\u2032Ni(\u03b7<jats:sup>3<\/jats:sup>\u2010P<jats:sub>4<\/jats:sub>RCl)][TEF] (R=Ph (<jats:bold>2\u2009f<\/jats:bold>), <jats:italic>t<\/jats:italic>Bu (<jats:bold>2\u2009g<\/jats:bold>)). In the reaction of <jats:bold>1<\/jats:bold> with [Br<jats:sub>2<\/jats:sub>P]<jats:sup>+<\/jats:sup>, an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp\u2032\u2032\u2032Ni}<jats:sub>2<\/jats:sub>(\u03bc,\u03b7<jats:sup>3<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>4<\/jats:sub>Br<jats:sub>3<\/jats:sub>)][TEF] (<jats:bold>3\u2009a<\/jats:bold>). A similar product [{Cp\u2032\u2032\u2032Ni}<jats:sub>2<\/jats:sub>(\u03bc,\u03b7<jats:sup>3<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>4<\/jats:sub>(2,2\u2032\u2010biphen)Cl)][GaCl<jats:sub>4<\/jats:sub>] (<jats:bold>3\u2009b<\/jats:bold>) is obtained, when <jats:bold>2\u2009d<\/jats:bold>[GaCl<jats:sub>4<\/jats:sub>] is kept in solution for prolonged times. Although the central structural motif of <jats:bold>2\u2009a<\/jats:bold>\u2013<jats:bold>g<\/jats:bold> consists of a \u201cbutterfly\u2010like\u201d folded P<jats:sub>4<\/jats:sub> ring attached to a {Cp\u2032\u2032\u2032Ni} fragment, the structures of <jats:bold>3\u2009a<\/jats:bold> and <jats:bold>3\u2009b<\/jats:bold> exhibit a unique asymmetrically substituted and distorted P<jats:sub>4<\/jats:sub> chain stabilised by two {Cp\u2032\u2032\u2032Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of <jats:bold>2\u2009a<\/jats:bold>\u2013<jats:bold>2\u2009g<\/jats:bold> and the bonding situation in <jats:bold>3\u2009a<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.202003291","type":"journal-article","created":{"date-parts":[[2020,9,30]],"date-time":"2020-09-30T08:22:36Z","timestamp":1601454156000},"page":"17165-17170","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Cationic Functionalisation by Phosphenium Ion Insertion"],"prefix":"10.1002","volume":"26","author":[{"given":"Christoph","family":"Riesinger","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luis","family":"D\u00fctsch","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  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