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Herein, we describe the reactivity of [P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    cations with cyclopentadienyl metal complexes. The reaction of [Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    Fe(\u03bc\u2010Br)]\n                    <jats:sub>2<\/jats:sub>\n                    (Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    =C\n                    <jats:sub>5<\/jats:sub>\n                    (C\n                    <jats:sub>6<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    \u20104\u2010Et)\n                    <jats:sub>5<\/jats:sub>\n                    ) with [P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    ][GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] (R=\n                    <jats:italic>i<\/jats:italic>\n                    Pr and 2,4,6\u2010Me\n                    <jats:sub>3<\/jats:sub>\n                    C\n                    <jats:sub>6<\/jats:sub>\n                    H\n                    <jats:sub>2<\/jats:sub>\n                    (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (\n                    <jats:bold>1\u2010R<\/jats:bold>\n                    , R=\n                    <jats:italic>i<\/jats:italic>\n                    Pr and Mes), showing an unsymmetric \u201cbutterfly\u201d structure. The same products\n                    <jats:bold>1\u2010R<\/jats:bold>\n                    were formed from K[Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    ] and [P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    ][GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ]. The cationic complexes [Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    Co(\u03b7\n                    <jats:sup>4<\/jats:sup>\n                    \u2010P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    )][GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] (\n                    <jats:bold>2\u2010R<\/jats:bold>\n                    [GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ], R=\n                    <jats:italic>i<\/jats:italic>\n                    Pr and Cy) and [(Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    Ni)\n                    <jats:sub>2<\/jats:sub>\n                    (\u03b7\n                    <jats:sup>3:3<\/jats:sup>\n                    \u2010P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    )][GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] (\n                    <jats:bold>3\u2010R<\/jats:bold>\n                    [GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ]) were obtained from [P\n                    <jats:sub>5<\/jats:sub>\n                    R\n                    <jats:sub>2<\/jats:sub>\n                    ][GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] and [Cp\n                    <jats:sup>Ar<\/jats:sup>\n                    M(\u03bc\u2010Br)]\n                    <jats:sub>2<\/jats:sub>\n                    (M=Co and Ni) as well as by using low\u2010valent \u201cCp\n                    <jats:sup>Ar<\/jats:sup>\n                    M\n                    <jats:sup>I<\/jats:sup>\n                    \u201d sources. Anion metathesis of\n                    <jats:bold>2\u2010R<\/jats:bold>\n                    [GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] and\n                    <jats:bold>3\u2010R<\/jats:bold>\n                    [GaCl\n                    <jats:sub>4<\/jats:sub>\n                    ] was achieved with Na[BArF\n                    <jats:sub>24<\/jats:sub>\n                    ]. The P\n                    <jats:sub>5<\/jats:sub>\n                    framework of the resulting salts\n                    <jats:bold>2\u2010R<\/jats:bold>\n                    [BArF\n                    <jats:sub>24<\/jats:sub>\n                    ] can be further functionalized with nucleophiles. Thus reactions with [Et\n                    <jats:sub>4<\/jats:sub>\n                    N]X (X=CN and Cl) give unprecedented cyano\u2010 and chloro\u2010functionalized complexes, while organo\u2010functionalization was achieved with CyMgCl.\n                  <\/jats:p>","DOI":"10.1002\/anie.201908998","type":"journal-article","created":{"date-parts":[[2019,9,26]],"date-time":"2019-09-26T22:34:13Z","timestamp":1569537253000},"page":"18584-18590","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Functionalization of Pentaphosphorus Cations by Complexation"],"prefix":"10.1002","volume":"58","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7250-5783","authenticated-orcid":false,"given":"Anup K.","family":"Adhikari","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christoph G. P.","family":"Ziegler","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kai","family":"Schwedtmann","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry TU Dresden  01062 Dresden Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Clemens","family":"Taube","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry TU Dresden  01062 Dresden Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7323-7816","authenticated-orcid":false,"given":"Jan. J.","family":"Weigand","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Food Chemistry TU Dresden  01062 Dresden Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4066-6483","authenticated-orcid":false,"given":"Robert","family":"Wolf","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry University of Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2019,11,6]]},"reference":[{"key":"e_1_2_2_1_1","first-page":"758","volume-title":"Lehrbuch der Anorganischen Chemie","author":"Wiberg N.","year":"2007"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60238a001"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100010e"},{"key":"e_1_2_2_5_2","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/B978-0-08-097774-4.00106-6","volume-title":"Comprehensive Inorganic Chemistry\u2005II, Vol.\u20051","author":"Weigand J. 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structurally related cationic bicyclo[1.1.0]pentaphosphane is described in Ref.\u2005[24]. Moreover several unsymmetrically substituted bicyclo[1.1.0]tetraphosphanes have been described recently; see Ref.\u2005[28h\u2013l]."},{"key":"e_1_2_2_101_1","unstructured":"[CpArCo(cod)] was synthesized by reducing [CpArCo(\u03bc-X)]2(X=Cl Br) with KC8in the presence of COD in THF; see the Supporting Information for a detailed procedure."},{"key":"e_1_2_2_102_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.6b00084"},{"key":"e_1_2_2_103_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200901472"},{"key":"e_1_2_2_104_1","unstructured":"It is noteworthy that such a second diastereomer was not observed for2-Cl-Cy(see Figure\u2005S93)."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201908998","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201908998","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201908998","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201908998","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,6]],"date-time":"2023-09-06T19:45:30Z","timestamp":1694029530000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201908998"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,11,6]]},"references-count":133,"journal-issue":{"issue":"51","published-print":{"date-parts":[[2019,12,16]]}},"alternative-id":["10.1002\/anie.201908998"],"URL":"https:\/\/doi.org\/10.1002\/anie.201908998","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.8940083.v1","asserted-by":"object"}]},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,11,6]]},"assertion":[{"value":"2019-07-18","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2019-11-06","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}