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This compound can be readily oxidized to the phosphorus(V) dihalo\u2010derivatives P(ONO)X<jats:sub>2<\/jats:sub> where X=Cl (<jats:bold>2<\/jats:bold>), Br (<jats:bold>3<\/jats:bold>) and I (<jats:bold>4<\/jats:bold>). Attempts at isolating the analogous difluoride through oxidation of <jats:bold>1<\/jats:bold> were unsuccessful yielding only the hydrofluoride P(ONO)(H)F (<jats:bold>5<\/jats:bold>), however P(ONO)F<jats:sub>2<\/jats:sub> (<jats:bold>6<\/jats:bold>) can be accessed via a halide exchange reaction of <jats:bold>2<\/jats:bold> with KF. Compound <jats:bold>2<\/jats:bold> can be employed as a precursor to novel cationic species through chloride ion displacement using strong Lewis bases. Thus, reaction of <jats:bold>2<\/jats:bold> with two or three molar equivalents of dimethylaminopyridine (DMAP) affords [P(ONO)(Cl)(DMAP)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> (<jats:bold>7<\/jats:bold>) and [P(ONO)(DMAP)<jats:sub>3<\/jats:sub>]<jats:sup>2+<\/jats:sup> (<jats:bold>8<\/jats:bold>). Reaction of <jats:bold>2<\/jats:bold> with the weaker bidentate base 2,2\u2032\u2010bipyridine (bipy) affords [P(ONO)(Cl)(bipy)]<jats:sup>+<\/jats:sup> (<jats:bold>9<\/jats:bold>), although this species was only accessible upon addition of a halide abstracting agent. The dicationic tris(pyridine) adduct [P(ONO)(py)<jats:sub>3<\/jats:sub>]<jats:sup>2+<\/jats:sup> (<jats:bold>10<\/jats:bold>) is also accessible by reaction of <jats:bold>4<\/jats:bold> with pyridine. Oxidation of <jats:bold>1<\/jats:bold> using oxygen gas proceeds slowly and allows for the observation of two compounds, a mixed valence dimeric phosphorus(III)\/phosphorus(V) compound [P(ONO)(\u03bc<jats:sup>2<\/jats:sup>\u2010O)(\u03bc<jats:sup>2<\/jats:sup>:\u03ba<jats:sup>1<\/jats:sup>,\u03ba<jats:sup>2<\/jats:sup>\u2010ONO)P] (<jats:bold>11<\/jats:bold>) and the fully oxidized species [P(ONO)(\u03bc<jats:sup>2<\/jats:sup>\u2010O)(\u03bc<jats:sup>2<\/jats:sup>:\u03ba<jats:sup>1<\/jats:sup>,\u03ba<jats:sup>2<\/jats:sup>\u2010ONO)P(O)] (<jats:bold>12<\/jats:bold>). Finally, reaction of <jats:bold>1<\/jats:bold> using KC<jats:sub>8<\/jats:sub> results in the dimerization of the putative radical anion [P(ONO)]<jats:sup>.\u2212<\/jats:sup> through formation of a P\u2212P bond to afford [P(ONO)]<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup> (<jats:bold>13<\/jats:bold>). Reactions with TEMPO result in the formation of the trigonal bipyramidal species P(ONO)(TEMPO)<jats:sub>2<\/jats:sub> (<jats:bold>14<\/jats:bold>).<\/jats:p>","DOI":"10.1002\/chem.201703119","type":"journal-article","created":{"date-parts":[[2017,9,2]],"date-time":"2017-09-02T11:22:34Z","timestamp":1504351354000},"page":"15455-15465","source":"Crossref","is-referenced-by-count":33,"title":["On the Redox Reactivity of a Geometrically Constrained Phosphorus(III) Compound"],"prefix":"10.1002","volume":"23","author":[{"given":"Thomas P.","family":"Robinson","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel","family":"De\u2005Rosa","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Oxford, Chemistry Research Laboratory  12 Mansfield Road Oxford OX1 3TA 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