{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T19:08:52Z","timestamp":1790795332372,"version":"4.1.0"},"reference-count":80,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2020,11,24]],"date-time":"2020-11-24T00:00:00Z","timestamp":1606176000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100004794","name":"Centre National de la Recherche Scientifique","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004794","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003768","name":"Universit\u00e9 de Strasbourg","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100003768","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["ANR-19-CE07-0020-01"],"award-info":[{"award-number":["ANR-19-CE07-0020-01"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2021,1,25]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The employment of the hexyl\u2010substituted anion [HexCB<jats:sub>11<\/jats:sub>Cl<jats:sub>11<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> allowed the synthesis of a Zn<jats:sup>II<\/jats:sup> species, Zn[HexCB<jats:sub>11<\/jats:sub>Cl<jats:sub>11<\/jats:sub>]<jats:sub>2<\/jats:sub>, <jats:bold>3<\/jats:bold>, in which the Zn<jats:sup>2+<\/jats:sup> cation is only weakly coordinated to two carborate counterions and that is soluble in low polarity organic solvents such as bromobenzene. DOSY NMR studies show the facile displacement of at least one of the counterions, and this near nakedness of the cation results in high catalytic activity in the hydrosilylation of 1\u2010hexene and 1\u2010methyl\u20101cyclohexene. Fluoride ion affinity (FIA) calculations reveal a solution Lewis acidity of <jats:bold>3<\/jats:bold> (FIA=262.1\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>) that is higher than that of the landmark Lewis acid B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> (FIA=220.5\u2005kJ\u2009mol<jats:sup>\u22121<\/jats:sup>). This high Lewis acidity leads to a high activity in catalytic CO<jats:sub>2<\/jats:sub> and Ph<jats:sub>2<\/jats:sub>CO reduction by Et<jats:sub>3<\/jats:sub>SiH and hydrogenation of 1,1\u2010diphenylethylene using 1,4\u2010cyclohexadiene as the hydrogen source. Compound <jats:bold>3<\/jats:bold> was characterized by multinuclear NMR spectroscopy, mass spectrometry, single crystal X\u2010ray diffraction, and DFT studies.<\/jats:p>","DOI":"10.1002\/anie.202012287","type":"journal-article","created":{"date-parts":[[2020,10,10]],"date-time":"2020-10-10T02:17:02Z","timestamp":1602296222000},"page":"2084-2088","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":33,"title":["Towards Naked Zinc(II) in the Condensed Phase: A Highly Lewis Acidic Zn<sup>II<\/sup> Dication Stabilized by Weakly Coordinating Carborate Anions"],"prefix":"10.1002","volume":"60","author":[{"given":"Nicolas","family":"Adet","sequence":"first","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David","family":"Specklin","sequence":"additional","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christophe","family":"Gourlaouen","sequence":"additional","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thibault","family":"Damiens","sequence":"additional","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"B\u00e9atrice","family":"Jacques","sequence":"additional","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0719-0620","authenticated-orcid":false,"given":"Rudolf J.","family":"Wehmschulte","sequence":"additional","affiliation":[{"name":"Chemistry Program Florida Institute of Technology  150 West University Boulevard Melbourne FL 32901-6975 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7393-286X","authenticated-orcid":false,"given":"Samuel","family":"Dagorne","sequence":"additional","affiliation":[{"name":"Institut de Chimie de Strasbourg CNRS-Universit\u00e9 de Strasbourg  1 rue Blaise Pascal 67000 Strasbourg France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,11,24]]},"reference":[{"key":"e_1_2_2_1_1","volume-title":"Acid Catalysis in Modern Organic Synthesis","author":"Yamamoto H.","year":"2009"},{"key":"e_1_2_2_2_1","unstructured":"Selected reviews:"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar100044s"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2009.01.012"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00672D"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201902877"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-019-0146-7"},{"key":"e_1_2_2_8_1","unstructured":"\u00a0"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201710782"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201710782"},{"key":"e_1_2_2_10_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2000.62"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.6b02677"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404833"},{"key":"e_1_2_2_13_1","unstructured":"\u00a0"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b01629"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b02136"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9805628"},{"key":"e_1_2_2_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar970230r"},{"key":"e_1_2_2_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20010119)7:2<490::AID-CHEM490>3.0.CO;2-I"},{"key":"e_1_2_2_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400096"},{"key":"e_1_2_2_20_1","unstructured":"\u00a0"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19623150303"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(00)83148-6"},{"key":"e_1_2_2_23_1","unstructured":"V. Nguyen-Duc New Salt-Like Dodecahydro-Closo-Dodecaborates and Efforts for the Partial Hydroxylation of [B12H12]2\u2212Anions. Ph.D. Thesis Universit\u00e4t Stuttgart 2009."},{"key":"e_1_2_2_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8DT00381E"},{"key":"e_1_2_2_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201502328"},{"key":"e_1_2_2_26_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)85732-0"},{"key":"e_1_2_2_27_1","author":"Dabringhaus P.","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"e_1_2_2_27_2","unstructured":"Angew. Chem. 2020"},{"key":"e_1_2_2_28_1","unstructured":"\u00a0"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0103557"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200353787"},{"key":"e_1_2_2_30_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200453787"},{"key":"e_1_2_2_31_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201300292"},{"key":"e_1_2_2_32_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0037-1610088"},{"key":"e_1_2_2_33_1","unstructured":"\u00a0"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic201921d"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201405662"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704382"},{"key":"e_1_2_2_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja060714v"},{"key":"e_1_2_2_38_1","unstructured":"The collected colorless solid was soluble enough for1H and11B\u2005NMR data which are consistent with the formation of Zn[CHB11Cl11]2."},{"key":"e_1_2_2_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2DT12431A"},{"key":"e_1_2_2_40_1","unstructured":"A PhBr adduct of a ZnIIorganocation was recently characterized in the solid state; see Ref.\u2005[20c]."},{"key":"e_1_2_2_41_1","unstructured":"DFT calculations also agree with dissociation of Zn[HexCB11Cl11]2to [Zn(HexCB11Cl11)]+and free [HexCB11Cl11]\u2212anion being energetically accessible under the studied conditions (\u0394G=34.7\u2005kJ\u2009mol\u22121)."},{"key":"e_1_2_2_42_1","unstructured":"Experimental estimation of the Lewis acidity of species3through the Guttmann\u2013Beckett method was inconclusive."},{"key":"e_1_2_2_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201802698"},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201203362"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201203362"},{"key":"e_1_2_2_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201605198"},{"key":"e_1_2_2_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201605198"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00451E"},{"key":"e_1_2_2_47_1","unstructured":"The formation of Zn\u22c5\u22c5\u22c5H\u2212SiEt3adduct [(HexCB11Cl11)Zn(HSiEt3)]+and free [HexCB11Cl11]\u2212is possible at low energy cost (\u0394G=25.9\u2005kJ\u2009mol\u22121). From the latter and in the presence of 1\u2005equiv of HSiEt3 HSiEt3heterolytic cleavage to the Zn\u2212H species [(HexCB11Cl11)Zn\u2212H] and the silylium cation [Et3Si\u22c5\u22c5\u22c5\u22c5H\u22c5\u22c5\u22c5\u22c5SiEt3]+requires no energy (\u0394G=0.0\u2005kJ\u2009mol\u22121)."},{"key":"e_1_2_2_48_1","unstructured":"29Si and1H\u2005NMR spectra of a 1\/23\/HSiEt3mixture (recorded at RT and at 90\u2009\u00b0C C6D5Br) only contain resonances for the starting reagents with no observation of Zn\u2212H and silylium moieties. IR data of a 1\/23\/HSiEt3mixture (RT PhBr) were inconclusive."},{"key":"e_1_2_2_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/b511344j"},{"key":"e_1_2_2_50_1","unstructured":"\u00a0"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9903003"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo991828a"},{"key":"e_1_2_2_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo016279z"},{"key":"e_1_2_2_54_1","unstructured":"\u00a0"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200636u"},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2063"},{"key":"e_1_2_2_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201502400"},{"key":"e_1_2_2_57_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201502400"},{"key":"e_1_2_2_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b01497"},{"key":"e_1_2_2_59_1","unstructured":"\u00a0"},{"key":"e_1_2_2_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201201282"},{"key":"e_1_2_2_60_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201201282"},{"key":"e_1_2_2_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.7b00716"},{"key":"e_1_2_2_62_1","unstructured":"For representative examples of Lewis acid-type mechanisms for CO2hydrosilylation with the initial functionalization of CO2to formate HCO2SiEt3and the subsequent formation of Et3SiOCH2OSiEt3 MeOSiEt3and eventually CH4 see Refs.\u2005[36] [37] and [20c]."},{"key":"e_1_2_2_63_1","unstructured":"\u00a0"},{"key":"e_1_2_2_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408346"},{"key":"e_1_2_2_64_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201408346"},{"key":"e_1_2_2_65_2","author":"Ritter F.","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"e_1_2_2_65_3","unstructured":"Angew. Chem. 2020"},{"key":"e_1_2_2_66_1","unstructured":"\u00a0"},{"key":"e_1_2_2_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404139"},{"key":"e_1_2_2_68_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201504941"},{"key":"e_1_2_2_68_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201504941"},{"key":"e_1_2_2_69_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202001376"},{"key":"e_1_2_2_70_1","unstructured":"Deposition Numbers 2025456 and 2025457(2and3) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures servicewww.ccdc.cam.ac.uk\/structures."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202012287","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202012287","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202012287","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,30]],"date-time":"2023-08-30T17:26:22Z","timestamp":1693416382000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202012287"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,11,24]]},"references-count":80,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2021,1,25]]}},"alternative-id":["10.1002\/anie.202012287"],"URL":"https:\/\/doi.org\/10.1002\/anie.202012287","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,11,24]]},"assertion":[{"value":"2020-09-09","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2020-11-24","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}