Systematic Access of Ternary Organotetrel-Copper Chalcogenide Clusters by [PhTE₃ ]^3- Anions (T=Si, Sn; E=S, Se).

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.

SUBMITTER: Rinn N 

PROVIDER: S-EPMC8453927 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature