Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT) 4 S 6 ], [(RSn) 3 S 4 ] 2− , [(RT) 2 (CuPPh 3 ) 6 S 6 ], and [(RSn) 6 (OMe) 6 Cu 2 S 6 ] 4− (R=C 2 H 4 COOH, CMe 2 CH 2 COMe; T=Ge, Sn)

Caged chalcogens : A series of novel, functionalized T n S m cages (T=Ge, Sn; n / m =4:6, 3:4) with terminal COO(H) or COMe groups were synthesized and show further reactivity toward Cu I complexes (an example of which is shown here) and to hydrazines. This led to the generation of functionalized Cu/T/S clusters or the formation of Schiff bases at the CO groups, respectively, with or without further fragmentation of the T/S core.A series of compounds comprising functionalized thiometallate cages [(RT) 4 S 6 ] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double‐decker (T=Sn) type structures or [(RSn) 3 S 4 ] 2− anionic defect heterocubanes were synthesized and their reactions with 1) transition‐metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COR ligands into CR(N‐NH 2 ) or CR(N‐NHPh) terminal groups, respectively. The report provides the proof‐of‐principle for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of chalcogenidometallate–organic hybrid compounds containing M/E semiconductor nodes, as an alternative to the so far most prominent M/O combination in metal–organic frameworks. DFT investigations deliver further insight in the peculiarities of Ge/S versus Sn/S precursors and their products.