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Chemical oxidation of [Cp(CO)<jats:sub>2<\/jats:sub>Mn\uf8feC(OEt)Fc] (<jats:bold>3\u2009a<\/jats:bold>) and isolation of the oxidised species <jats:bold>[3\u2009a][PF<jats:sub>6<\/jats:sub>]<\/jats:bold> possessing a Mn<jats:sup>II<\/jats:sup> centre proved possible below \u221230\u2009\u00b0C in dichloromethane solution. The ESR spectrum of the transiently stable radical cation, <jats:bold>[3\u2009a][PF<jats:sub>6<\/jats:sub>]<\/jats:bold>, confirmed the presence of a low\u2010spin Mn<jats:sup>II<\/jats:sup> centre characterized by a rhombic <jats:italic>g<\/jats:italic> tensor (<jats:italic>g<\/jats:italic><jats:sub>x<\/jats:sub>=1.975, <jats:italic>g<\/jats:italic><jats:sub>y<\/jats:sub>=2.007 and <jats:italic>g<\/jats:italic><jats:sub>z<\/jats:sub>=2.130) in frozen dichloromethane at 77\u2005K with <jats:sup>55<\/jats:sup>\u2005Mn hyperfine coupling constants <jats:italic>A<\/jats:italic><jats:sub>1<\/jats:sub>, <jats:italic>A<\/jats:italic><jats:sub>2<\/jats:sub> and <jats:italic>A<\/jats:italic><jats:sub>3<\/jats:sub> of 115, 33 and 43\u2005G, respectively. Electrochemical studies demonstrated the influence of the Ar substituent on the oxidation potential. All complexes showed that the redox potentials of carbene double bond reduction and Mn<jats:sup>I<\/jats:sup> oxidation were dependent on the type of Ar group, but only <jats:bold>3\u2009b<\/jats:bold> showed resolved oxidations for the two Mn<jats:sup>I<\/jats:sup> centres. Surprisingly, Mn<jats:sup>I<\/jats:sup> oxidation occurs at lower potentials than ferrocenyl oxidation. Density functional theory (DFT) calculations were carried out to delineate the nature of the species involved in the oxidation and reduction processes and clearly confirm that oxidation of Mn<jats:sup>I<\/jats:sup> is favoured over that of ferrocene.<\/jats:p>","DOI":"10.1002\/chem.201304711","type":"journal-article","created":{"date-parts":[[2014,3,18]],"date-time":"2014-03-18T18:56:47Z","timestamp":1395169007000},"page":"4974-4985","source":"Crossref","is-referenced-by-count":20,"title":["Redox Behaviour of Cymantrene Fischer Carbene Complexes in Designing Organometallic Multi\u2010tags"],"prefix":"10.1002","volume":"20","author":[{"given":"Daniela I.","family":"Bezuidenhout","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Belinda","family":"van der Westhuizen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Pieter J.","family":"Swarts","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Teshica","family":"Chatturgoon","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Orde Q.","family":"Munro","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Israel","family":"Fern\u00e1ndez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jannie C.","family":"Swarts","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,3,18]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0492653"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bioelechem.2004.07.005"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0898-8838(03)55004-8"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/om700609z"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00303-X"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0956-5663(01)00313-X"},{"key":"e_1_2_6_8_2","unstructured":"\u00a0"},{"key":"e_1_2_6_9_2","first-page":"3431","volume":"27","author":"Shago R. 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