{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T23:47:47Z","timestamp":1788392867427,"version":"build-2803163510"},"reference-count":78,"publisher":"Wiley","issue":"45","license":[{"start":{"date-parts":[[2016,10,5]],"date-time":"2016-10-05T00:00:00Z","timestamp":1475625600000},"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":[[2016,11,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Strong oxidizing agents often contain fluorine and are not compatible with substrates forming strong element\u2013fluorine bonds. Therefore, there is need for new strong oxidizers. Cyclic voltammetric measurements on the weakly coordinating anion [Me<jats:sub>3<\/jats:sub>NB<jats:sub>12<\/jats:sub>Cl<jats:sub>11<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> in liquid SO<jats:sub>2<\/jats:sub> revealed an oxidation wave at +2.59\u2005V versus Fc<jats:sup>0\/+<\/jats:sup>. The oxidation of Na[Me<jats:sub>3<\/jats:sub>NB<jats:sub>12<\/jats:sub>Cl<jats:sub>11<\/jats:sub>] with AsF<jats:sub>5<\/jats:sub> in liquid sulfur dioxide gives the boron\u2010cluster\u2010based radical Me<jats:sub>3<\/jats:sub>NB<jats:sub>12<\/jats:sub>Cl<jats:sub>11<\/jats:sub><jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> as a dark blue solid in quantitative yield. The radical was characterized by vibrational, NMR, and EPR spectroscopy and by its crystal structure. To explore the potential of the radical Me<jats:sub>3<\/jats:sub>NB<jats:sub>12<\/jats:sub>Cl<jats:sub>11<\/jats:sub><jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> to act as a strong oxidizing agent, it was reacted with different compounds having high ionization energies. Thianthrene (ionization energy 7.8\u2005eV) and hexabromobenzene (8.8\u2005eV) were oxidized to the corresponding cations. The reaction with elemental iodine (9.3\u2005eV) gave the [I<jats:sub>5<\/jats:sub>]<jats:sup>+<\/jats:sup> cation. These reactive cations are stabilized in the solid state by the weakly coordinating anion [Me<jats:sub>3<\/jats:sub>NB<jats:sub>12<\/jats:sub>Cl<jats:sub>11<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>, which was formed as a reduced product in the oxidation reactions.<\/jats:p>","DOI":"10.1002\/chem.201603924","type":"journal-article","created":{"date-parts":[[2016,10,12]],"date-time":"2016-10-12T13:10:13Z","timestamp":1476277813000},"page":"16032-16036","source":"Crossref","is-referenced-by-count":24,"title":["The Me<sub>3<\/sub>NB<sub>12<\/sub>Cl<sub>11<\/sub><sup>.<\/sup> Radical: A Strong One\u2010Electron Oxidizing Agent"],"prefix":"10.1002","volume":"22","author":[{"given":"Philipp","family":"Bertocco","sequence":"first","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Mathematik und Naturwissenschaften Anorganische Chemie Bergische Universit\u00e4t Wuppertal  Gau\u00dfstrasse 20 42119 Wuppertal 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Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,10,5]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196804331"},{"key":"e_1_2_2_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19680801202"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199702731"},{"key":"e_1_2_2_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090318"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2009.06.012"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00279a078"},{"key":"e_1_2_2_6_1","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470421604"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2005.07.008"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00230-7"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(99)00191-5"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201201262"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201201262"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.289.5476.101"},{"key":"e_1_2_2_13_1","unstructured":"\u00a0"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940053x"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00274a065"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201307161"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201307161"},{"key":"e_1_2_2_17_1","unstructured":"\u00a0"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-08-097774-4.00125-X"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900159e"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/B415425H"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar970230r"},{"key":"e_1_2_2_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50080a009"},{"key":"e_1_2_2_23_1","unstructured":"\u00a0"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9622160"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic301236s"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066247z"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010504)40:9<1664::AID-ANIE16640>3.0.CO;2-O"},{"key":"e_1_2_2_27_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010504)113:9<1713::AID-ANGE17130>3.0.CO;2-T"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/a905406e"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201001374"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5QI00263J"},{"key":"e_1_2_2_31_1","unstructured":"\u00a0"},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001374v"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0475205"},{"key":"e_1_2_2_34_1","unstructured":"\u00a0"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004755"},{"key":"e_1_2_2_35_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201004755"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201304405"},{"key":"e_1_2_2_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b02256"},{"key":"e_1_2_2_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201202475"},{"key":"e_1_2_2_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja001573e"},{"key":"e_1_2_2_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja111035k"},{"key":"e_1_2_2_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201100448"},{"key":"e_1_2_2_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201403625"},{"key":"e_1_2_2_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/b821030f"},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404487"},{"key":"e_1_2_2_45_1","first-page":"317","author":"Castellon\u00e8se 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Soc. Chim. Fr."},{"key":"e_1_2_2_46_1","unstructured":"Synthesis of Me3NB12Cl11.: AsF5(1.53\u2005g 9\u2005mmol) and ca. 5\u2005mL SO2were condensed at \u2212196\u2009\u00b0C onto Na[Me3NB12Cl11] (1.01\u2005g 1.7\u2005mmol) in an H-shaped reaction vessel equipped with J.Young Teflon-in glass valves and an incorporated fine frit. Upon warming to room temperature the reaction mixture turned dark blue after a few minutes. The reaction mixture was stirred at room temperature overnight to complete the reaction. Subsequently the blue solution was filtered over the fine frit to seperate it from a white insoluble by-product (Na[AsF6] as was shown by IR analysis). After removal of all volatiles in vacuum the product Me3NB12Cl11.remained as a dark blue solid in quantitative yield. A full spectroscopic characterization is given in the Supporting Information Section\u2005S3."},{"key":"e_1_2_2_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200803493"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200803493"},{"key":"e_1_2_2_48_1","unstructured":"Alternatively the EPR spectrum of solid Me3NB12Cl11.shown in Figure\u20052 was simulated very successfully assuming rhombic symmetry with a rather small and unresolvedganisotropy \u0394gusingg1=2.037 g2=2.016 g3=2.010 and Gaussian line widths of 30 37 and 37\u2005G; resulting in \u0394g=g1\u2212g3=0.027 andgav=2.021 (Figure\u2005S4 in the Supporting Information)."},{"key":"e_1_2_2_49_1","unstructured":"Crystallographic details are given in the Supporting Information Section\u2005S8. CCDC\u20051457508 (Me3NB12Cl11.) 1457509 ([C12H8S2][Me3NB12Cl11]\u22c5SO2) 1470337 ([AsCl4][Me3NB12Cl11]\u22c5SO2) 1470338 ([I5][Me3NB12Cl11]\u22c5SO2) and 1470339 ([C6Br6][Me3NB12Cl11] contain the supplementary crystallographic data for this paper. These data are provided free of charge byThe Cambridge Crystallographic Data Centre. Further details of the crystal structure investigation of [I3]2[B12Cl12] may be obtained from FIZ Karlsruhe 76344 Eggenstein-Leopoldshafen Germany (fax: (+49)7247-808-666; e-mail: crysdata@fiz-karlsruhe.de on quoting the deposition number CSD-431181."},{"key":"e_1_2_2_50_1","unstructured":"NIST Chemistry WebBook http:\/\/webbook.nist.gov\/chemistry\/ 2016."},{"key":"e_1_2_2_51_1","unstructured":"\u00a0"},{"key":"e_1_2_2_52_2","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1515\/znb-2009-0201","volume":"64","author":"Beck J.","year":"2009","journal-title":"Z. Naturforsch. Sect. 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