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This indicates that an in situ rearrangement of the inorganic core takes place even without initial formation of anionic fragments. The use of [Cu(PPh<jats:sub>3<\/jats:sub>)<jats:sub>3<\/jats:sub>Cl] or [Cu(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>] as reactants yielded the ternary clusters [(CuPPh<jats:sub>3<\/jats:sub>)<jats:sub>4<\/jats:sub>(PhSn)<jats:sub>18<\/jats:sub>Cu<jats:sub>6<\/jats:sub>S<jats:sub>31<\/jats:sub>Cl<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>) and [{Cu(PPh<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(PhSn)<jats:sub>3<\/jats:sub>(SnCl)S<jats:sub>8<\/jats:sub>] (<jats:bold>2<\/jats:bold>), respectively. Whereas <jats:bold>1<\/jats:bold> represents the largest neutral Cu\/Sn\/S cluster known to date, compound <jats:bold>2<\/jats:bold>, which is the first example of a ternary Cu\/Sn\/E (E=S, Se) cluster containing copper in the +II oxidation state, may be viewed as a very early stage of cluster formation. Apparently, the presence of Cu<jats:sup>II<\/jats:sup> inhibits effective cluster growth, which rationalizes the lack of such species so far. The two ternary clusters exhibit very similar optical absorption energies despite their markedly different cluster sizes. According to time\u2010dependent DFT calculations, this is due to different characters of the electronic excitation in the triplet compound <jats:bold>2<\/jats:bold>, as compared to the excitation of the closed shell cluster <jats:bold>1<\/jats:bold>, which serve to compensate for the different extensions of the clusters.<\/jats:p>","DOI":"10.1002\/chem.201806407","type":"journal-article","created":{"date-parts":[[2019,1,2]],"date-time":"2019-01-02T06:45:23Z","timestamp":1546411523000},"page":"2486-2490","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Transition\u2010Metal\u2010Induced Rearrangement of [(PhSn)<sub>4<\/sub>S<sub>6<\/sub>] Towards Ternary Cu<sup>I<\/sup>\/Sn\/S or Cu<sup>II<\/sup>\/Sn\/S Clusters"],"prefix":"10.1002","volume":"25","author":[{"given":"Eike","family":"Dornsiepen","sequence":"first","affiliation":[{"name":"Fachbereich Chemie und Wissenschaftliches Zentrum f\u00fcr 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