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To get access to larger metalloid cluster compounds of Group\u200514, the disproportionation reaction of metastable monohalide solutions, accessible through a preparative co\u2010condensation reaction, proved to be quite successful. As the identity of the subvalent halides within the metastable solutions were yet unknown the reaction course from a monohalide precursor to a metalloid cluster was mostly unidentified. This might change now, as a first subhalide cluster [Ge<jats:sub>14<\/jats:sub>Br<jats:sub>8<\/jats:sub>(Et<jats:sub>3<\/jats:sub>P)<jats:sub>4<\/jats:sub>] could be characterized, being the first trapped intermediate of the disproportionation reaction of Group\u200514 subhalides. All these aspects are included within this Minireview, together with a short historical overview, dealing with the development of the preparative co\u2010condensation technique out of the matrix isolation technique, being the essential first step of the synthesis of metastable monohalide solutions of the heavier Group\u200514 elements Ge and Sn.<\/jats:p>","DOI":"10.1002\/chem.201804318","type":"journal-article","created":{"date-parts":[[2018,10,18]],"date-time":"2018-10-18T03:55:46Z","timestamp":1539834946000},"page":"144-157","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Halides of the Heavier Group\u200514 Homologues Germanium, Tin, and Lead\u2014A Journey through Unusual Compounds and Oxidation States"],"prefix":"10.1002","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0062-8845","authenticated-orcid":false,"given":"Tanja","family":"Kunz","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle 18 72076 T\u00fcbingen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7719-7476","authenticated-orcid":false,"given":"Andreas","family":"Schnepf","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle 18 72076 T\u00fcbingen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2018,12,11]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500368"},{"key":"e_1_2_8_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500368"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/9780470669266.ch5"},{"key":"e_1_2_8_3_1","unstructured":"\u00a0"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja000990o"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20021004)41:19<3532::AID-ANIE3532>3.0.CO;2-4"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20021004)114:19<3682::AID-ANGE3682>3.0.CO;2-6"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1007\/430_2015_5004"},{"key":"e_1_2_8_7_1","unstructured":"\u00a0"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900375g"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/B516379J"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00703"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201412050"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201412050"},{"key":"e_1_2_8_12_1","unstructured":"\u00a0"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7CC09063C"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8DT01009A"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-5088(88)90098-7"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01264a504"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19542750102"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9807341"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198900551"},{"key":"e_1_2_8_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19891010133"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00041a063"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/prac.18870360119"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01423a008"},{"key":"e_1_2_8_23_1","first-page":"523","volume":"220","author":"K\u00f6hler J.","year":"2005","journal-title":"Z. 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