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Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. We now establish Raman spectroscopy as a reliable probe to assign for the first time the presence of discrete, endohedrally filled clusters in intermetallic phases. The ternary precursor alloys with nominal compositions \u201cK<jats:sub>5<\/jats:sub>Co<jats:sub>1.2<\/jats:sub>Ge<jats:sub>9<\/jats:sub>\u201d and \u201cK<jats:sub>4<\/jats:sub>Ru<jats:sub>3<\/jats:sub>Sn<jats:sub>7<\/jats:sub>\u201d exhibit characteristic bonding modes originating from metal atoms in the center of polyhedral clusters, thus revealing that filled clusters are present in these alloys. We report also on the structural characterization of [Co@Ge<jats:sub>9<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> (<jats:bold>1a<\/jats:bold>) and [Ru@Sn<jats:sub>9<\/jats:sub>]<jats:sup>6\u2212<\/jats:sup> (<jats:bold>2a<\/jats:bold>) obtained from solutions of the respective alloys.<\/jats:p>","DOI":"10.1002\/anie.201907127","type":"journal-article","created":{"date-parts":[[2019,7,12]],"date-time":"2019-07-12T13:19:34Z","timestamp":1562937574000},"page":"12908-12913","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":33,"title":["Metallocages for Metal Anions: Highly Charged [Co@Ge<sub>9<\/sub>]<sup>5\u2212<\/sup> and [Ru@Sn<sub>9<\/sub>]<sup>6\u2212<\/sup> Clusters Featuring Spherically Encapsulated Co<sup>1\u2212<\/sup> and Ru<sup>2\u2212<\/sup> Anions"],"prefix":"10.1002","volume":"58","author":[{"given":"Benedikt J. L.","family":"Witzel","sequence":"first","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstrasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wilhelm","family":"Klein","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstrasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jasmin V.","family":"Dums","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstrasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marina","family":"Boyko","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstrasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9460-8882","authenticated-orcid":false,"given":"Thomas F.","family":"F\u00e4ssler","sequence":"additional","affiliation":[{"name":"Department Chemie Technische Universit\u00e4t M\u00fcnchen  Lichtenbergstrasse 4 85747 Garching Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,8,21]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.intermet.2004.02.010"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.intermet.2004.11.001"},{"key":"e_1_2_2_4_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0365110X58000487"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/crat.201200494"},{"key":"e_1_2_2_6_1","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19390520102"},{"key":"e_1_2_2_8_2","first-page":"329","author":"Klemm W.","year":"1959","journal-title":"Proc. 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The incorporation of a d10metal atom (Ni) or ion (Co\u2212or Cu+) does not change this electron count."},{"key":"e_1_2_2_63_1","unstructured":"Both new compounds turned out to contain hydroxide as an unintentional impurity most likely introduced by contaminated batches of NH3(l). The hydroxide anion is coordinated by a distorted square pyramid of five K+ions with the hydroxide H atom located at the basal face of the pyramid. These K+ions are additionally coordinated by 3\u20135 ammonia molecules each so a [K5(OH)(NH3)11]4+complex cation is formed. The same arrangement has been found for example in K5[OH][Ge9]\u22c511\u2009NH3[30]and in K5[OH][Sn9]\u22c511\u2009NH3.[31]Structural details are given in the Supporting Information."},{"key":"e_1_2_2_64_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(01)00321-6"},{"key":"e_1_2_2_65_1","unstructured":"\u00a0"},{"key":"e_1_2_2_66_2","first-page":"433","volume":"41","author":"Schubert K. P. H.","year":"1950","journal-title":"Z. 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