{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T07:01:53Z","timestamp":1788505313550,"version":"build-2803163510"},"reference-count":80,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2012,12,11]],"date-time":"2012-12-11T00:00:00Z","timestamp":1355184000000},"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":[[2013,1,28]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1\u2010carba\u2010<jats:italic>closo<\/jats:italic>\u2010dodecaborate anions, [1\u2010R\u2010CB<jats:sub>11<\/jats:sub>X<jats:sub>5<\/jats:sub>Y<jats:sub>6<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0\/def2\u2010TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas\u2010phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square\u2010wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15\u20132.85\u2005V versus Fc<jats:sup>0\/+<\/jats:sup>), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (\u22121.93 to \u22123.32\u2005V versus Fc<jats:sup>0\/+<\/jats:sup>). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes.<\/jats:p>","DOI":"10.1002\/chem.201202475","type":"journal-article","created":{"date-parts":[[2012,12,11]],"date-time":"2012-12-11T10:24:06Z","timestamp":1355221446000},"page":"1784-1795","source":"Crossref","is-referenced-by-count":47,"title":["Quantum\u2010Chemical and Electrochemical Investigation of the Electrochemical Windows of Halogenated Carborate Anions"],"prefix":"10.1002","volume":"19","author":[{"given":"Ren\u00e9 T.","family":"Boer\u00e9","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christoph","family":"Bolli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maik","family":"Finze","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander","family":"Himmelspach","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carsten","family":"Knapp","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tracey L.","family":"Roemmele","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,12,11]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00019a005"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19931050709"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199310251"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar970230r"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300620"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300620"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr050548u"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900159e"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.289.5476.101"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1073540"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja058581l"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja962294n"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201100448"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0007511"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/aoc.407"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/b802374c"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar1000023"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0013-4686(98)00157-1"},{"key":"e_1_2_6_17_2","first-page":"23","volume":"31","author":"King B. T.","year":"2001","journal-title":"Chem. Innov."},{"key":"e_1_2_6_18_2","unstructured":"J.Michl B.King J.Zbynek Weakly NucleophilicAnions WO 9631519 (A1) 1996."},{"key":"e_1_2_6_19_2","unstructured":"S. H.Strauss S. V.Ivanov Fluorinated Amino Polyhedral BorateCompounds US 6335466 B1 2002."},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0344160"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0733179"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9622160"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066247z"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja111035k"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0475205"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701606p"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50122a016"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00062a018"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja964328x"},{"key":"e_1_2_6_30_2","unstructured":"The hexahalogenated anions [1\u2010H\u2010CB11H5X6]\u2212(X=Cl Br I) were described in Ref.\u2005[3] as being electrochemically inert against anodic oxidation in CH2Cl2up to a solvent limit of about 2.0\u2005V versus Fc0\/+ but we were unable to locate an original study that confirmed this statement."},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9614935"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic2026939"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic202660d"},{"key":"e_1_2_6_34_2","first-page":"245","volume-title":"Electrochemical Methods","author":"Bard A. J.","year":"2001"},{"key":"e_1_2_6_34_3","doi-asserted-by":"publisher","DOI":"10.1142\/p783"},{"key":"e_1_2_6_35_2","first-page":"496","volume-title":"Electrochemical Methods","author":"Bard A. J.","year":"2001"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1039\/b821030f"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200701136"},{"key":"e_1_2_6_37_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200701136"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270111035165"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1039\/c001555e"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja060714v"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1039\/B410929E"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(99)00285-6"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic980110v"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540120914"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/b922720b"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701398u"},{"key":"e_1_2_6_47_2","unstructured":"Calculations at the latter level by Michl et\u2005al. resulted in a different structure for theCsA\u2032 symmetrical 1\u2010H\u2010CB11H11.radical in which the B12\uf8ffH bond showed a strong off\u2010axis bend.[23]Attempts to reproduce the structure of theCsA\u2032 symmetrical 1\u2010H\u2010CB11H11.radical with an off\u2010axis bend at the PBE0\/def2\u2010TZVPP level failed but instead resulted in a secondCsA\u2032 symmetrical isomer (II) which was slightly higher (0.43\u2005kJ\u2009mol\u22121) in energy than the firstCsA\u2032 isomer (I). Also for theA\u2032\u2032 state a second isomer (A\u2032\u2032 (II)) existed as a true minimum on the potential\u2010energy surface. Obviously the potential\u2010energy surface is very shallow for 1\u2010H\u2010CB11H11.and the energy differences between the different isomers are very small. Thus for the calculation of ionization energies it seems reasonable to assume that the calculation of possible further isomers for the halogenated 1\u2010carba\u2010closo\u2010dodecaborates would not change these general results."},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102960"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201004755"},{"key":"e_1_2_6_49_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004755"},{"key":"e_1_2_6_50_2","unstructured":"S. V.Ivanov W. J.Casteel\u2005Jr. G. P.Pez M.Ulman Polyfluorinated boron cluster anions for lithiumelectrolytes EP 1513215\u2005A2 2005."},{"key":"e_1_2_6_51_2","volume-title":"Electrochemical Methods: Fundamentals and Applications","author":"Bard A. J.","year":"2001"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp809105f"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00297a010"},{"key":"e_1_2_6_54_2","volume-title":"CRC Handbook of Chemistry and Physics","year":"2007"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-73740-7"},{"key":"e_1_2_6_56_2","unstructured":"The electrochemical oxidation and reduction of [1\u2010H\u2010CB11I11]\u2212showed different behavior compared to the other anions. This difference might be a result of the weak B\uf8ffI bond as well as their different electronic structures. The different behavior of the periodinated anion needs further investigation and therefore all of the values regarding this anion should be treated tentatively."},{"key":"e_1_2_6_57_2","unstructured":"Scanning to even more positive potentials resulted in a second oxidation in the SWV; for details see the Supporting Information Section\u2005S1.2.1."},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940053x"},{"key":"e_1_2_6_59_2","unstructured":"1\u2010H\u2010CB11I11]\u2212 [1\u2010H\u2010CB11Br11]\u2212 and [1\u2010Me\u2010CB11Br11]\u2212displayed complex behavior in their cathodic scans at more\u2010negative potentials. We attribute this complex behavior to follow\u2010on reactions that are likely induced by halide elimination from the dianions. The nature of these follow\u2010on reactions was not investigated further. For details see the Supporting Information Section\u2005S1.2.2."},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00122a003"},{"key":"e_1_2_6_61_2","unstructured":"Two exceptions in Figure\u20057 warrant further discussion. First the measured oxidation potential of the [1\u2010H\u2010CB11Br11]\u2212anion is lower (by 0.09\u2005V in the CV and 0.01\u2005V in the SWV) than that of [1\u2010H\u2010CB11Cl11]\u2212 whereas the opposite is predicted by the calculations (0.05\u2005eV higher). The second fact concerns the order of the anions with the lowest oxidation potential. Whilst the calculations predict that [1\u2010H\u2010CB11I11]\u2212is the easiest to oxidize followed by [1\u2010H\u2010CB11H11]\u2212and [1\u2010H\u2010CB11Me5Br6]\u2212 the experimental results show that [1\u2010H\u2010CB11H11]\u2212(Epa1(CV)=2.35\u2005V) is harder to oxidize than [1\u2010H\u2010CB11I11]\u2212(Epa1(CV)=2.15\u2005V) and [1\u2010H\u2010CB11Me5Br6]\u2212(Epa1(CV)=2.29\u2005V). These differences may simply be due to their solvation energies which are not taken into account in the gas\u2010phase calculations. The small [1\u2010H\u2010CB11H11]\u2212anion gains even in a less\u2010coordinating solvent like SO2 more solvation energy than the larger halogenated anions. Therefore it is feasible that the additional solvation energy makes the oxidation of [1\u2010H\u2010CB11H11]\u2212more unfavorable compared to that of the two larger anions."},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja980026e"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1135\/cccc20011238"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja973827a"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic9805628"},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1135\/cccc19860819"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0118800"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(95)00838-U"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050244"},{"key":"e_1_2_6_70_2","unstructured":"\u00a0"},{"key":"e_1_2_6_71_2","unstructured":"TURBOMOLE Version 6.10 and 6.20 COSMOlogic;"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(89)85118-8"},{"key":"e_1_2_6_73_2","unstructured":"Gaussian 09 Revision\u2005B.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery \u2005Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov T. Keith R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels O. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2010."},{"key":"e_1_2_6_74_2","unstructured":"http:\/\/bse.pnl.gov\/bse\/portal."},{"key":"e_1_2_6_75_2","unstructured":"ChemCraft Version 1.6 http:\/\/www.chemcraftprog.com."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201202475","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201202475","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:35:56Z","timestamp":1760301356000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201202475"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2012,12,11]]},"references-count":80,"journal-issue":{"issue":"5","published-print":{"date-parts":[[2013,1,28]]}},"alternative-id":["10.1002\/chem.201202475"],"URL":"https:\/\/doi.org\/10.1002\/chem.201202475","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2012,12,11]]}}}