Syntheses, Crystal Structures, and Reactivity of [ en H] 4 [Sn 2 Se 6 ]· en , [ en H] 4 [Sn 2 Te 6 ]· en and [ en H] 4 [Sn 2 S 6 ]: Known Anions within Novel Coordination Spheres obtained by Novel Synthesis Routes

The hexachalcogenodistannates K 6 [Sn III 2 Se 6 ] or Li 4 [Sn IV 2 Te 6 ]·8 en were recently reported to simultaneously act as mild oxidants and chalcogenide sources in reactions with CoCl 2 /LiCp* (Cp* = pentamethylcyclopentadienide) while the Sn—E (E = Se, Te) fragment is not kept in the products, e.g. [(Cp*Co) 3 ( μ 3 ‐Se) 2 ], [(Cp*Co) 3 ( μ 3 ‐Se) 2 ][Cl 2 Co( μ 2 ‐Cl) 2 Li(thf) 2 ] or [(Cp*Co) 4 ( μ 3 ‐Te) 4 ]. In search of related reagents with possibly different reaction behavior, we isolated and crystallographically characterized isotypic compounds [ en H] 4 [Sn IV 2 Se 6 ] en ( 1 ), and [ en H] 4 [Sn IV 2 Te 6 ]· en ( 2 ) ( en = 1, 2‐diaminoethane), that result from an uncommon disproportion/re‐arrangement reaction: distannate(III) K 6 [Sn 2 E 6 ] (E = Se, Te) was reacted with en ·2HCl to yield 1 or 2 under disproportion of Sn III to Sn II and Sn IV . Another pathway was necessary to synthesize the respective but solvent‐free thiostannate [ en H] 4 [Sn IV 2 S 6 ] ( 3 ), since the phase “K 6 [Sn 2 S 6 ]” is unknown. This second method started out from SnCl 4 ·2THF and S(SiMe 3 ) 2 in en solution. However, using E(SiMe 3 ) 2 (E = Se, Te) instead of S(SiMe 3 ) 2 , 1 and 2 are also obtained this way. 1—3 are the first chalcogenostannates that exhibit exclusively [ en H] + counterions. The compounds were characterized by means of X‐ray crystallography and NMR spectroscopy. They seem to be suitable for reactions towards group 8‐10 metal complexes. Preliminary experiments indicate that the binary anions 1 — 3 coordinated by 1‐aminoethylammonium ions react more slowly compared to the anionic phases tested until now.