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Treatment of <jats:bold>1<\/jats:bold> with two equivalents of potassium hydride gave access to octametallic precursor complex [H<jats:sub>2<\/jats:sub><jats:sup>Ph2S<\/jats:sup>L<jats:sup>AP<\/jats:sup>K<jats:sub>2<\/jats:sub>(thf)]<jats:sub>4<\/jats:sub> (<jats:bold>2<\/jats:bold>), which reacted with FeCl<jats:sub>3<\/jats:sub> to yield iron(III) complex [H<jats:sub>2<\/jats:sub><jats:sup>Ph2S<\/jats:sup>L<jats:sup>AP<\/jats:sup>FeCl] (<jats:bold>3<\/jats:bold>). Employing Fe[N(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>3<\/jats:sub> for a direct reaction with <jats:bold>1<\/jats:bold> led to ligand rearrangement through C\uf8ffS bond cleavage and thiolate formation, finally yielding [HL<jats:sup>AP<\/jats:sup>Fe] (<jats:bold>5<\/jats:bold>). Upon exposure to O<jats:sub>2<\/jats:sub>, <jats:bold>3<\/jats:bold> and <jats:bold>5<\/jats:bold> are oxidized through formal hydrogen\u2010atom abstraction from the ligand NH units to form [<jats:sup>Ph2S<\/jats:sup>L<jats:sup>SQ<\/jats:sup>FeCl] (<jats:bold>4<\/jats:bold>) and [L<jats:sup>SQ<\/jats:sup>Fe] (<jats:bold>6<\/jats:bold>) featuring two or one coordinated iminosemiquinone moieties, respectively. M\u00f6ssbauer measurements demonstrated that the iron centers remain in their +III oxidation states. Compounds <jats:bold>3<\/jats:bold> and <jats:bold>5<\/jats:bold> were tested with respect to their potential as models for the catechol dioxygenase. Thus, they were treated with 3,5\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u2010catechol, triethylamine and O<jats:sub>2<\/jats:sub>. It turned out that the iron\u2013catecholate complexes react with O<jats:sub>2<\/jats:sub> in dichloromethane at ambient conditions through C\uf8ffC bond cleavage mainly forming extradiol cleavage products. Intradiol products are only side products and quinone formation becomes negligible. This observation has been rationalized by a dissociation of two donor functions upon coordination of the catecholate.<\/jats:p>","DOI":"10.1002\/chem.201304535","type":"journal-article","created":{"date-parts":[[2014,3,13]],"date-time":"2014-03-13T06:42:00Z","timestamp":1394692920000},"page":"4721-4735","source":"Crossref","is-referenced-by-count":32,"title":["A Novel Pentadentate Redox\u2010Active Ligand and Its Iron(III) Complexes: Electronic Structures and O<sub>2<\/sub> Reactivity"],"prefix":"10.1002","volume":"20","author":[{"given":"Ramona","family":"Metzinger","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Serhiy","family":"Demeshko","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christian","family":"Limberg","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,3,13]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/350087a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9519896"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19980817)110:16<2340::AID-ANGE2340>3.0.CO;2-C"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980904)37:16<2217::AID-ANIE2217>3.0.CO;2-D"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.279.5350.537"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0162-0134(01)00214-8"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.05.021"},{"key":"e_1_2_6_8_2","unstructured":"\u00a0"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2010.01.009"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2010.12.006"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35228A"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/0471227110.ch2"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1183281"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201103233"},{"key":"e_1_2_6_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201103233"},{"key":"e_1_2_6_16_2","unstructured":"Review:"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204100"},{"key":"e_1_2_6_17_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204100"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1515\/BC.2005.118"},{"key":"e_1_2_6_19_2","unstructured":"\u00a0"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic2003832"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja030124m"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic061106j"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molcata.2006.02.045"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700354"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200700413"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201200389"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020628n"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic050557l"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0365110X56001790"},{"key":"e_1_2_6_31_2","unstructured":"\u00a0"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100785a001"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(94)00035-B"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1039\/a804134b"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/b816136b"},{"key":"e_1_2_6_35_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201203201"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049579i"},{"key":"e_1_2_6_37_2","first-page":"287","volume-title":"Physical Methods in Bioinorganic Chemistry. 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