Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

The synthesis of new functionalized organotin‐chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R 1, 2 Sn) 3 S 4 Cl] ( 1 , 2 ), [((R 2 Sn) 2 SnS 4 ) 2 (μ‐S) 2 ] ( 3 ), [(R 1, 2 Sn) 3 Se 4 ][SnCl 3 ] ( 4, 5 ), and [Li(thf) n ][(R 3 Sn)(HR 3 Sn) 2 Se 4 Cl] ( 6 ), in which R 1 =CMe 2 CH 2 C(O)Me, R 2 =CMe 2 CH 2 C(NNH 2 )Me, and R 3 =CH 2 CH 2 COO, are based on defect heterocubane scaffolds, as shown by X‐ray diffraction, 119 Sn NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4 , 5 , and 6 constitute the first examples of defect heterocubane‐type metal‐chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R 1 SnCl 2 ) 2 (μ‐S)] ( 7 ) and [(R 1 SnCl) 2 (μ‐S) 2 ] ( 8 ), which were isolated and helped to understand the stepwise formation of compounds 1 – 6 .