{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T19:55:10Z","timestamp":1760385310180,"version":"build-2065373602"},"reference-count":98,"publisher":"Wiley","issue":"41","license":[{"start":{"date-parts":[[2013,8,20]],"date-time":"2013-08-20T00:00:00Z","timestamp":1376956800000},"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":[[2013,10,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The 1:3 reactions of the alkoxy arenes 1,4\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub> and 1,4\u2010F<jats:sub>2<\/jats:sub>\u20102,5\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub> with TaF<jats:sub>5<\/jats:sub> in chloroform at 40\u201350\u2009\u00b0C resulted in formation in about 35\u2009% yield of the long\u2010lived radical cation salts [1,4\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>][Ta<jats:sub>2<\/jats:sub>F<jats:sub>11<\/jats:sub>] (<jats:bold>2\u2009a<\/jats:bold>) and [1,4\u2010F<jats:sub>2<\/jats:sub>\u20102,5\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub>][Ta<jats:sub>2<\/jats:sub>F<jats:sub>11<\/jats:sub>] (<jats:bold>2\u2009b<\/jats:bold>), respectively. The non\u2010alkoxy\u2010substituted [arene][M<jats:sub>2<\/jats:sub>X<jats:sub>11<\/jats:sub>] [M=Ta, X=F: arene=C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>Me (<jats:bold>2\u2009c<\/jats:bold>), 1,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>Me<jats:sub>2<\/jats:sub> (<jats:bold>2\u2009d<\/jats:bold>), C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>F (<jats:bold>2\u2009e<\/jats:bold>), C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>NO<jats:sub>2<\/jats:sub> (<jats:bold>2\u2009f<\/jats:bold>); M=Nb, X=F: arene=C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>Me (<jats:bold>4\u2009a<\/jats:bold>), 1,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>Me<jats:sub>2<\/jats:sub> (<jats:bold>4\u2009b<\/jats:bold>), C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>F (<jats:bold>4\u2009c<\/jats:bold>), C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>NO<jats:sub>2<\/jats:sub> (<jats:bold>4\u2009d<\/jats:bold>); M=Ta, X=Cl: arene=1,4\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>Me<jats:sub>2<\/jats:sub> (<jats:bold>5<\/jats:bold>)] were obtained from the 3:1 reactions of MX<jats:sub>5<\/jats:sub> with the appropriate arene in chloroform at temperatures in the range 40\u201390\u2009\u00b0C. Compounds <jats:bold>2<\/jats:bold>\u2013<jats:bold>5<\/jats:bold> were detected by EPR spectroscopy (in CHCl<jats:sub>3<\/jats:sub>) at room temperature, and their gas\u2010phase structures were optimized by DFT calculations. Formation of the M<jats:sup>IV<\/jats:sup> species [MX<jats:sub>4<\/jats:sub>(NCMe)<jats:sub>2<\/jats:sub>] [M=Ta, X=F (<jats:bold>3\u2009a<\/jats:bold>); M=Nb, X=F (<jats:bold>3\u2009b<\/jats:bold>); M=Ta, X=Cl (<jats:bold>3\u2009c<\/jats:bold>)] was ascertained by EPR spectroscopy on solutions obtained by treatment of the reaction mixtures with acetonitrile. Non\u2010selective reactions occurred upon combination of 1,4\u2010F<jats:sub>2<\/jats:sub>\u20102,5\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub> with AgNbF<jats:sub>6<\/jats:sub> (in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>) and 1,4\u2010(MeO)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub> with SbF<jats:sub>5<\/jats:sub>.<\/jats:p>","DOI":"10.1002\/chem.201301552","type":"journal-article","created":{"date-parts":[[2013,8,20]],"date-time":"2013-08-20T04:47:10Z","timestamp":1376974030000},"page":"13962-13969","source":"Crossref","is-referenced-by-count":25,"title":["Long\u2010Lived Radical Cation Salts Obtained by Interaction of Monocyclic Arenes with Niobium and Tantalum Pentahalides at Room Temperature: EPR and DFT Studies"],"prefix":"10.1002","volume":"19","author":[{"given":"Fabio","family":"Marchetti","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Guido","family":"Pampaloni","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Calogero","family":"Pinzino","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2013,8,20]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1071\/CH9580104"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567740868004279"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567740872003280"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0567740872003292"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201205478"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201205478"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2005.11.002"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0166-1280(98)00038-4"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/a705393b"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-0728(96)04942-X"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1149\/1.2048521"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00088a003"},{"volume-title":"Organic Electrochemistry","year":"1991","author":"Lund H.","key":"e_1_2_6_14_2"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00173a025"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1973.141"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/j39700002613"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)88843-2"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00987a037"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00975a020"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1139\/v66-225"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01073a043"},{"key":"e_1_2_6_23_2","unstructured":"\u00a0"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CC14592D"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2dt31453c"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/b907774j"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1039\/b810210d"},{"key":"e_1_2_6_28_2","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201001572"},{"key":"e_1_2_6_29_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201001572"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2010.11.042"},{"key":"e_1_2_6_31_2","unstructured":"\u00a0"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9028408"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1697200"},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102960"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200900666"},{"key":"e_1_2_6_36_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200900666"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00276a039"},{"key":"e_1_2_6_38_2","unstructured":"The pentafluorides of niobium and tantalum have tetranuclear structures in the solid state while tantalum pentachloride is dinuclear.[4a]Such compounds are referred to by the empirical formulas MX5throughout this paper."},{"key":"e_1_2_6_39_2","unstructured":"\u00a0"},{"key":"e_1_2_6_40_2","first-page":"990","volume-title":"Chemistry of the Elements","author":"Greenwood N. 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In fact the stepwise additions of MeCN to3\u2009aleading to [TaF4(NCMe)3] and [TaF4(NCMe)4] are thermodynamically highly disfavoured processes (calculated \u0394Gvalues are 96.95 and 88.97\u2005kJ\u2009mol\u22121 respectively)."},{"key":"e_1_2_6_49_2","unstructured":"All of the attempts to cleanly isolate3\u2009ain the solid state failed."},{"key":"e_1_2_6_50_2","unstructured":"The calculatedgisovalue for3\u2009ais 1.9571. The calculatedgisovalues for [TaF4(NCMe)3] and [TaF4(NCMe)4] are 1.9560 and 1.9563 respectively."},{"key":"e_1_2_6_51_2","first-page":"633","volume-title":"Advanced Inorganic Chemistry","author":"Cotton F. A.","year":"1999"},{"key":"e_1_2_6_52_2","first-page":"1","volume":"26","author":"Drobot D. V.","year":"1981","journal-title":"Russ. J. Inorg. Chem."},{"key":"e_1_2_6_53_2","unstructured":"\u00a0"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39910000841"},{"key":"e_1_2_6_55_2","unstructured":"G. P.Hagen D. 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