{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T00:52:14Z","timestamp":1760316734940,"version":"build-2065373602"},"reference-count":52,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2008,4,11]],"date-time":"2008-04-11T00:00:00Z","timestamp":1207872000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2008,5,29]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Metal(III)\u2013polypyridine complexes [M(NN)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup> (M=Ru or Fe; NN=bipyridine (bpy), phenanthroline (phen), or 4,7\u2010dimethylphenanthroline (Me<jats:sub>2<\/jats:sub>\u2010phen)) oxidize the nitrosylpentaaquachromium(III) ion, [Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup>, with an overall 4:1 stoichiometry, 4\u2009[Ru(bpy)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>+[Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup>+2\u2009H<jats:sub>2<\/jats:sub>O\u21924\u2009[Ru(bpy)<jats:sub>3<\/jats:sub>]<jats:sup>2+<\/jats:sup>+[Cr<jats:sub>aq<\/jats:sub>]<jats:sup>3+<\/jats:sup>+NO<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup>+4\u2009H<jats:sup>+<\/jats:sup>. The kinetics follow a mixed second\u2010order rate law, \u2212d[[M(NN)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>]\/d<jats:italic>t<\/jats:italic>=<jats:italic>nk<\/jats:italic>[[M(NN)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>][[Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup>], in which <jats:italic>k<\/jats:italic> represents the rate constant for the initial one\u2010electron transfer step, and <jats:italic>n<\/jats:italic>=2\u20134 depending on reaction conditions and relative rates of the first and subsequent steps. With [Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup> in excess, the values of <jats:italic>nk<\/jats:italic> are 283\u2009<jats:sc>M<\/jats:sc><jats:sup>\u22121<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup> ([Ru(bpy)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>), 7.4 ([Ru(Me<jats:sub>2<\/jats:sub>\u2010phen)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>), and 5.8 ([Fe(phen)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup>). In the proposed mechanism, the one\u2010electron oxidation of [Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup> releases NO, which is further oxidized to nitrite, <jats:italic>k<\/jats:italic>=1.04\u00d710<jats:sup>6<\/jats:sup>\u2009<jats:sc>M<\/jats:sc><jats:sup>\u22121<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup>, 6.17\u00d710<jats:sup>4<\/jats:sup>, and 1.12\u00d710<jats:sup>4<\/jats:sup> with the three respective oxidants. Further oxidation yields the observed nitrate. The kinetics of the first step show a strong correlation with thermodynamic driving force. Parallels were drawn with oxidative homolysis of a superoxochromium(III) ion, [Cr<jats:sub>aq<\/jats:sub>OO]<jats:sup>2+<\/jats:sup>, to gain insight into relative oxidizability of coordinated NO and O<jats:sub>2<\/jats:sub>, and to address the question of the \u201coxidation state\u201d of coordinated NO in [Cr<jats:sub>aq<\/jats:sub>NO]<jats:sup>2+<\/jats:sup>.<\/jats:p>","DOI":"10.1002\/chem.200701750","type":"journal-article","created":{"date-parts":[[2008,4,11]],"date-time":"2008-04-11T05:48:58Z","timestamp":1207892938000},"page":"4906-4912","source":"Crossref","is-referenced-by-count":6,"title":["Oxidative Homolysis of a Nitrosylchromium Complex"],"prefix":"10.1002","volume":"14","author":[{"given":"Wenjing","family":"Song","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreja","family":"Bakac","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,5,20]]},"reference":[{"doi-asserted-by":"publisher","key":"e_1_2_6_1_2","DOI":"10.1038\/327524a0"},{"doi-asserted-by":"publisher","key":"e_1_2_6_2_2","DOI":"10.1021\/cr000074t"},{"doi-asserted-by":"publisher","key":"e_1_2_6_3_2","DOI":"10.1021\/cr0000271"},{"doi-asserted-by":"publisher","key":"e_1_2_6_4_2","DOI":"10.1021\/cr950056p"},{"doi-asserted-by":"publisher","key":"e_1_2_6_5_2","DOI":"10.1016\/S0031-6997(25)06663-3"},{"volume-title":"Nitric Oxide. 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