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This anion is found to be derived from the formerly reported [Sn<jats:sub>4<\/jats:sub>Bi<jats:sub>4<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup> by the formal substitution of one tin atom by bismuth. In contrast, the extraction of \u201cRbSn<jats:sub>2<\/jats:sub>\/Rb<jats:sub>3<\/jats:sub>Bi<jats:sub>2<\/jats:sub>\u201d in liquid ammonia yielded the anion [Sn<jats:sub>3<\/jats:sub>Bi<jats:sub>3<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> in the compound Rb<jats:sub>6<\/jats:sub>[Sn<jats:sub>3<\/jats:sub>Bi<jats:sub>3<\/jats:sub>][Sn<jats:sub>4<\/jats:sub>]<jats:sub>1\/4<\/jats:sub>\u22c56.75\u2009NH<jats:sub>3<\/jats:sub>. The structural correlation of the two novel clusters indicates that [Sn<jats:sub>3<\/jats:sub>Bi<jats:sub>3<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> might be an intermediate of the reaction pathway to [Sn<jats:sub>3<\/jats:sub>Bi<jats:sub>5<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup> and [Sn<jats:sub>4<\/jats:sub>Bi<jats:sub>4<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup>. Each cluster is investigated by means of the electron localization function and further characterization was performed by using ESI\u2010MS.<\/jats:p>","DOI":"10.1002\/open.201600037","type":"journal-article","created":{"date-parts":[[2016,5,25]],"date-time":"2016-05-25T20:19:32Z","timestamp":1464207572000},"page":"306-310","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["A Step in Between: [Sn<sub>3<\/sub>Bi<sub>3<\/sub>]<sup>5\u2212<\/sup> and Its Structural Relationship to [Sn<sub>3<\/sub>Bi<sub>5<\/sub>]<sup>3\u2212<\/sup> and [Sn<sub>4<\/sub>Bi<sub>4<\/sub>]<sup>4\u2212<\/sup>"],"prefix":"10.1002","volume":"5","author":[{"given":"Ute","family":"Friedrich","sequence":"first","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie und Pharmazie Universit\u00e4t Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nikolaus","family":"Korber","sequence":"additional","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie und Pharmazie Universit\u00e4t Regensburg  Universit\u00e4tsstra\u00dfe 31 93053 Regensburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,5,25]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201001630"},{"key":"e_1_2_2_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201001630"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500387w"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b008123j"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200801249"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/aoc.433"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja992269s"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00452a020"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/a906586e"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic502158e"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2009.03.082"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201310456"},{"key":"e_1_2_2_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201310456"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.200600108"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39880001027"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.199762301146"},{"key":"e_1_2_2_16_1","unstructured":"\u00a0"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc35318k"},{"key":"e_1_2_2_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902163"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00200a034"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic000925f"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201300943"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja200520c"},{"key":"e_1_2_2_23_1","unstructured":"\u00a0"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.201000458"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00139a008"},{"key":"e_1_2_2_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200902249"},{"key":"e_1_2_2_27_1","unstructured":"\u00a0"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00374a018"},{"key":"e_1_2_2_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic102152e"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0DT00918K"},{"key":"e_1_2_2_31_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc35380f"},{"key":"e_1_2_2_32_1","unstructured":"\u00a0"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201005496"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja203302t"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja209226b"},{"key":"e_1_2_2_36_1","unstructured":"CrysAlisPro Software Version 1.171.37.35 Agilent Technologies UK Ltd. 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