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Updated: Nov 8, 2025

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Systematic Access of Ternary Organotetrel-Copper Chalcogenide Clusters by [PhTE3 ]3- Anions (T=Si, Sn; E=S, Se)
Niklas Rinn1, Lukas Guggolz1, Han Yu Hou1
1Fachbereich Chemie, Philipps Universität Marburg, Hans-Meerwein Straße 4, 35037, Marburg, Germany.
Abstract:
Fragmentation reactions of organotetrel chalcogenide heteroadamantane-type clusters [(PhT)4 E6 ] (T/E=Si/S (1); Si/Se; Sn/S, and Sn/Se) by addition of the corresponding sodium chalcogenide gave salts of the general formula Na3 [PhTE3 ], with T/E=Si/S (2); Si/Se (3); Sn/S (A); Sn/Se (4). Reaction of these salts with [Cu(PPh3 )3 Cl] gave a series of organotetrel-copper chalcogenide clusters [(CuPPh3 )6 (PhTE3 )2 ] with T/E=Si/S; (5), Si/Se (6), Sn/S (7) and Sn/Se (8). Compounds 5-8 share a common structural motif with two intact {PhTE3 } units coordinating a Cu6 moiety, which was previously reported with other ligands, and for the Sn and Ge congeners only. If the Sn/Se reaction system was allowed to crystallize more slowly, single crystals of compound [(CuPPh3 )6 (PhSnSe3 )3 Cu3 SnSe] (9) were obtained, which are based on a larger cluster structure. Hence, 9 might form from 8 through incorporation of additional cluster fragments. The experimentally and quantum chemically determined optical properties were compared to related clusters.
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