{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T19:08:08Z","timestamp":1791313688698,"version":"4.3.1"},"reference-count":112,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T00:00:00Z","timestamp":1762732800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,1,9]]},"abstract":"Abstract<\/jats:title>\n \n We disclose the synthesis and properties of [M(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n (M\u00a0=\u00a0Cu, Ag, Au) with the first gold\u2010based anion [Au(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n . The\n nido<\/jats:italic>\n \u2010[B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n ]\n 4\u2212<\/jats:sup>\n ligand stabilizes complexes with copper, silver, and gold in the highest known oxidation state +V. The relative stability of [M\n +V<\/jats:sup>\n (\n nido<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n X\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n , [M\n +III<\/jats:sup>\n (\n nido<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n X\n 11<\/jats:sub>\n )(\n closo<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n X\n 11<\/jats:sub>\n )]\n 3\u2212<\/jats:sup>\n , and [M\n +I<\/jats:sup>\n (\n closo<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n X\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n isomers (X\u00a0=\u00a0H, F) was calculated at the DFT level. Unlike for [Cu(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n and [Au(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n , in case of [Ag(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n , we discovered the equilibrium between the kinetically stable [Ag\n +V<\/jats:sup>\n (\n nido<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n (\u03b7\n 5<\/jats:sup>\n ) and kinetically labile [Ag\n +I<\/jats:sup>\n (\n closo<\/jats:italic>\n \u2010B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n (\u03b7\n 2<\/jats:sup>\n ) by X\u2010ray diffraction. The isomerization of the Ag complex shows signs of Ag(V)\u2013Ag(I) redox processes. When a crystal is cooled, a phase transition occurs at 110\u2013130\u00a0K in which the coordination of the ligands on the silver changes from \u03b7\n 5<\/jats:sup>\n to \u03b7\n 2<\/jats:sup>\n . The phase transition is reversible and upon heating to 170\u00a0K, the \u03b7\n 2<\/jats:sup>\n to \u03b7\n 5<\/jats:sup>\n coordination is transformed. The reaction of [M(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n with HF leads to the partial substitution of hydrogen atoms by fluorine atoms to form [M(B\n 11<\/jats:sub>\n H\n 11\u2212x<\/jats:sub>\n F\n x<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n (M\u00a0=\u00a0Cu, Au; x\u00a0\u2248\u00a04). We synthesized 18 compounds containing [M(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\n 3\u2212<\/jats:sup>\n (M\u00a0=\u00a0Cu, Ag, Au) and their derivatives, followed by structural determination (X\u2010ray crystallography). XANES data confirm the high oxidation state of Cu in K\n 3<\/jats:sub>\n [Cu(B\n 11<\/jats:sub>\n H\n 11<\/jats:sub>\n )\n 2<\/jats:sub>\n ]\u00b75H\n 2<\/jats:sub>\n O.\n <\/jats:p>","DOI":"10.1002\/anie.202519283","type":"journal-article","created":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T09:32:11Z","timestamp":1762767131000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["The Biicosahedral Complex Anions [M(B\n 11<\/sub>\n H\n 11<\/sub>\n )\n 2<\/sub>\n ]\n 3\u2212<\/sup>\n (M\u00a0=\u00a0Cu, Ag, Au): Synthesis and Unexpected Low\u2010Temperature Phase Transition of [Ag(\u03b7\n 5<\/sup>\n \u2010B\n 11<\/sub>\n H\n 11<\/sub>\n )\n 2<\/sub>\n ]\n 3\u2212<\/sup>\n to [Ag(\u03b7\n 2<\/sup>\n \u2010B\n 11<\/sub>\n H\n 11<\/sub>\n )\n 2<\/sub>\n ]\n 3\u2212<\/sup>"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0350-3231","authenticated-orcid":false,"given":"Eduard","family":"Bernhardt","sequence":"first","affiliation":[{"name":"Chair of Inorganic Chemistry University of Wuppertal Gau\u00dfstr. 20 42119 Wuppertal Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-3228-0064","authenticated-orcid":false,"given":"Tanja","family":"Knuplez","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Institut f\u00fcr nachhaltige Chemie & Katalyse mit Bor (ICB) Julius\u2010Maximilians\u2010Universit\u00e4t W\u00fcrzburg Am Hubland 97074 W\u00fcrzburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7288-3004","authenticated-orcid":false,"given":"Tobias","family":"Preitschopf","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Institut f\u00fcr nachhaltige Chemie & Katalyse mit Bor (ICB) Julius\u2010Maximilians\u2010Universit\u00e4t W\u00fcrzburg Am Hubland 97074 W\u00fcrzburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5895-1608","authenticated-orcid":false,"given":"Andreas","family":"Drichel","sequence":"additional","affiliation":[{"name":"Chair of Inorganic Chemistry University of Wuppertal Gau\u00dfstr. 20 42119 Wuppertal Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5888-8952","authenticated-orcid":false,"given":"Bj\u00f6rn","family":"Beele","sequence":"additional","affiliation":[{"name":"Chair of Inorganic Chemistry University of Wuppertal Gau\u00dfstr. 20 42119 Wuppertal Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2660-8105","authenticated-orcid":false,"given":"Alexey","family":"Maximenko","sequence":"additional","affiliation":[{"name":"National Synchrotron Radiation Centre SOLARIS Jagiellonian University Krak\u00f3w, Ma\u0142opolska Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6098-7148","authenticated-orcid":false,"given":"Maik","family":"Finze","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Institut f\u00fcr nachhaltige Chemie & Katalyse mit Bor (ICB) Julius\u2010Maximilians\u2010Universit\u00e4t W\u00fcrzburg Am Hubland 97074 W\u00fcrzburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4452-1831","authenticated-orcid":false,"given":"Adam","family":"Slabon","sequence":"additional","affiliation":[{"name":"Chair of Inorganic Chemistry University of Wuppertal Gau\u00dfstr. 20 42119 Wuppertal Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,11,10]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.191204503113"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19360691241"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF01492209"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01097a049"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01097a054"},{"key":"e_1_2_8_6_1","unstructured":"V. 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