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Here, we show that the rare\u2010earth dinitrogen complexes [{(Cp\n                    <jats:sup>ttt<\/jats:sup>\n                    )\n                    <jats:sub>2\u00a0<\/jats:sub>\n                    M}\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\u20101,2\u2010N\n                    <jats:sub>2<\/jats:sub>\n                    )] (M\u00a0=\u00a0Y, Gd; Cp\n                    <jats:sup>ttt<\/jats:sup>\n                    \u00a0=\u00a01,2,4\u2010tri(\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl)cyclopentadienyl), reductively cleave P\n                    <jats:sub>4<\/jats:sub>\n                    to give a homologous series of phosphorus anions of decreasing nuclearity, that is, [{(Cp\n                    <jats:sup>ttt<\/jats:sup>\n                    )\n                    <jats:sub>2\u00a0<\/jats:sub>\n                    M}\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\u2010P\n                    <jats:sub>4<\/jats:sub>\n                    )] (\n                    <jats:bold>1<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    ), [{(Cp\n                    <jats:sup>ttt<\/jats:sup>\n                    )\n                    <jats:sub>2\u00a0<\/jats:sub>\n                    M}\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\u2010\u03b7\n                    <jats:sup>2<\/jats:sup>\n                    :\u03b7\n                    <jats:sup>2<\/jats:sup>\n                    \u2010P\n                    <jats:sub>2<\/jats:sub>\n                    )] (\n                    <jats:bold>2<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    ), and [{(Cp\n                    <jats:sup>ttt<\/jats:sup>\n                    )\n                    <jats:sub>2\u00a0<\/jats:sub>\n                    M}\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\u2010P)] (\n                    <jats:bold>3<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    ). Structural, spectroscopic, and computational studies show that\n                    <jats:bold>1<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    contains a bicyclobutane\u2010like [P\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2013<\/jats:sup>\n                    ligand, whereas\n                    <jats:bold>2<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    features a side\u2010on coordinated [P\u2550P]\n                    <jats:sup>2\u2013<\/jats:sup>\n                    ligand, and\n                    <jats:bold>3<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    comprises a monatomic P\n                    <jats:sup>2\u2013<\/jats:sup>\n                    ligand formulated as a phosphorus\u2010centered radical with\n                    <jats:italic>S<\/jats:italic>\n                    \u00a0=\u00a01\/2. The EPR spectrum of\n                    <jats:bold>\n                      3\n                      <jats:sub>Y<\/jats:sub>\n                    <\/jats:bold>\n                    confirms hyperfine coupling to\n                    <jats:sup>31<\/jats:sup>\n                    P and\n                    <jats:sup>89<\/jats:sup>\n                    Y, while magnetic measurements on\n                    <jats:bold>\n                      3\n                      <jats:sub>Gd<\/jats:sub>\n                    <\/jats:bold>\n                    reveal strong antiferromagnetic exchange between the Gd\n                    <jats:sup>3+<\/jats:sup>\n                    ions and the radical ligand. Density functional theory supports a three\u2010center \u03c0\u2010type M\u2013P\u2013M interaction in\n                    <jats:bold>3<\/jats:bold>\n                    <jats:bold>\n                      <jats:sub>M<\/jats:sub>\n                    <\/jats:bold>\n                    , with the unpaired spin localized primarily on phosphorus and only weak delocalization onto the metal centers. These findings represent progressive fragmentation of P\n                    <jats:sub>4<\/jats:sub>\n                    to diatomic and monatomic phosphorus anions by rare\u2010earth reagents, thereby extending the chemistry of multiply bonded phosphorus and persistent phosphorus radicals into the rare\u2010earth series.\n                  <\/jats:p>","DOI":"10.1002\/anie.6643873","type":"journal-article","created":{"date-parts":[[2026,6,21]],"date-time":"2026-06-21T15:52:27Z","timestamp":1782057147000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Reductive Activation of White Phosphorus to [P\n                    <sub>4<\/sub>\n                    ]\n                    <sup>2\u2013<\/sup>\n                    , [P\n                    <sub>2<\/sub>\n                    ]\n                    <sup>2\u2013<\/sup>\n                    , and a Formal P\n                    <sup>2\u2013<\/sup>\n                    Radical by Rare\u2010Earth Dinitrogen Complexes"],"prefix":"10.1002","volume":"65","author":[{"given":"Arpan","family":"Mondal","sequence":"first","affiliation":[{"name":"Department of Chemistry School of Life Sciences University of Sussex  Brighton U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6020-0309","authenticated-orcid":false,"given":"Richard A.","family":"Layfield","sequence":"additional","affiliation":[{"name":"Department of Chemistry School of Life Sciences University of Sussex  Brighton 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