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The reaction of Na[<jats:italic>cyclo<\/jats:italic>\u2010P<jats:sub>5<\/jats:sub>] with alkynes and nitriles was studied by means of DFT methods, which suggested a concerted mechanism for the formation of <jats:bold>2<\/jats:bold>\u2009<jats:bold>a<\/jats:bold> and <jats:bold>4<\/jats:bold>\u2009<jats:bold>b<\/jats:bold>. The anions <jats:bold>2<\/jats:bold>\u2009<jats:bold>a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>, <jats:bold>4<\/jats:bold>\u2009<jats:bold>a,b<\/jats:bold>, and <jats:bold>6<\/jats:bold> coordinate in an <jats:italic>\u03b7<\/jats:italic><jats:sup>5<\/jats:sup>\u2010fashion towards Fe<jats:sup>II<\/jats:sup> to give the sandwich (aza)phosphametallocenes <jats:bold>3<\/jats:bold>\u2009<jats:bold>a<\/jats:bold>\u2013<jats:bold>c<\/jats:bold>, <jats:bold>5<\/jats:bold>\u2009<jats:bold>a,b<\/jats:bold> and <jats:bold>7<\/jats:bold> in moderate to good yields. The new compounds were characterized by means of multinuclear NMR spectroscopy, single\u2010crystal X\u2010ray diffraction and cyclic voltammetry.<\/jats:p>","DOI":"10.1002\/chem.202203056","type":"journal-article","created":{"date-parts":[[2022,10,9]],"date-time":"2022-10-09T22:03:59Z","timestamp":1665353039000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Reactivity of Sodium Pentaphospholide Na[<i>cyclo<\/i>\u2010P<sub>5<\/sub>] towards C\u2261E (E=C, N, P) Triple Bonds"],"prefix":"10.1002","volume":"28","author":[{"given":"Andrey","family":"Petrov","sequence":"first","affiliation":[{"name":"Institute of Chemistry and Biochemistry Freie Universit\u00e4t Berlin  Fabeckstr. 34\/36 14195 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lawrence","family":"Conrad","sequence":"additional","affiliation":[{"name":"Institute of Chemistry and Biochemistry Freie Universit\u00e4t Berlin  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