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The frontier orbitals of the radical <jats:bold>2\u2009a<\/jats:bold> are indicative of a stable \u03c0\u2010allylic system that is only marginally influenced by the d orbitals of the two tungsten atoms. The SOMO and the corresponding spin density distribution of the radical <jats:bold>2\u2009a<\/jats:bold> show that the unpaired electron is preferentially located at the two equivalent terminal phosphorus atoms, which has been confirmed by EPR spectroscopy. The protonated derivative of <jats:bold>2\u2009a<\/jats:bold>, the complex [(CO)<jats:sub>5<\/jats:sub>W(\u03bc,\u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>As(H)Mes*<jats:sub>2<\/jats:sub>)W(CO)<jats:sub>4<\/jats:sub>] (<jats:bold>6\u2009a<\/jats:bold>) is formed during chromatographic workup, whereas the additional products [Mes*P\uf8fePMes*{W(CO)<jats:sub>5<\/jats:sub>}] as the <jats:italic>Z<\/jats:italic>\u2010isomer (<jats:bold>3<\/jats:bold>) and the <jats:italic>E<\/jats:italic>\u2010isomer (<jats:bold>4<\/jats:bold>), and [As<jats:sub>2<\/jats:sub>{W(CO)<jats:sub>5<\/jats:sub>}<jats:sub>3<\/jats:sub>] (<jats:bold>5<\/jats:bold>) are produced as a result of a decomposition reaction of radical <jats:bold>2\u2009a<\/jats:bold>. Reduction of radical <jats:bold>2\u2009a<\/jats:bold> yields the stable anion [(CO)<jats:sub>5<\/jats:sub>W(\u03bc,\u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>AsMes*<jats:sub>2<\/jats:sub>)W(CO)<jats:sub>4<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> in <jats:bold>7\u2009a<\/jats:bold>, whereas upon oxidation the corresponding cationic complex [(CO)<jats:sub>5<\/jats:sub>W(\u03bc,\u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>2<\/jats:sub>AsMes*<jats:sub>2<\/jats:sub>)W(CO)<jats:sub>4<\/jats:sub>][SbF<jats:sub>6<\/jats:sub>] (<jats:bold>8\u2009a<\/jats:bold>) is formed, which is only stable at low temperatures in solution. Compounds <jats:bold>2\u2009a<\/jats:bold>, <jats:bold>7\u2009a<\/jats:bold>, and <jats:bold>8\u2009a<\/jats:bold> represent the hitherto elusive complexed redox congeners of the diphospha\u2010arsa\u2010allyl system. The analogous oxidation of the triphosphaallyl radical [(CO)<jats:sub>5<\/jats:sub>W(\u03bc,\u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010 P<jats:sub>3<\/jats:sub>Mes*<jats:sub>2<\/jats:sub>)W(CO)<jats:sub>4<\/jats:sub>] (<jats:bold>2\u2009b<\/jats:bold>) also leads to an allyl cation, which decomposes under CH activation to the phosphine derivative [(CO)<jats:sub>5<\/jats:sub>W{\u03bc,\u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>\u2010P<jats:sub>3<\/jats:sub>(Mes*)(C<jats:sub>5<\/jats:sub>H<jats:sub>2<\/jats:sub><jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>C(CH<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>)}W(CO)<jats:sub>4<\/jats:sub>] (<jats:bold>9<\/jats:bold>), in which a CH bond of a methyl group of the Mes* substituent has been activated. All new products have been characterized by NMR spectrometry and IR spectroscopy, and compounds <jats:bold>2\u2009a<\/jats:bold>, <jats:bold>3<\/jats:bold>, <jats:bold>6\u2009a<\/jats:bold>, <jats:bold>7\u2009a<\/jats:bold>, and <jats:bold>9<\/jats:bold> by X\u2010ray diffraction analysis.<\/jats:p>","DOI":"10.1002\/chem.201000418","type":"journal-article","created":{"date-parts":[[2010,5,20]],"date-time":"2010-05-20T05:50:50Z","timestamp":1274334650000},"page":"7488-7495","source":"Crossref","is-referenced-by-count":15,"title":["The Complexed 1,3\u2010Diphospha\u20102\u2010Arsaallyl Radical and Its Cationic and Anionic Derivatives"],"prefix":"10.1002","volume":"16","author":[{"given":"Markus","family":"Stubenhofer","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christian","family":"Kuntz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michael","family":"Bodensteiner","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ulrich","family":"Zenneck","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Marek","family":"Sierka","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Manfred","family":"Scheer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,6,25]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/a909109b"},{"key":"e_1_2_6_2_2","first-page":"355","volume":"7","author":"Giese B.","year":"1994","journal-title":"Chemtracts: Org. 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