Solvothermal Reactions between Barium, Manganese, and Tellurium in Methylamine – the Formation of Polytellurides and Unexpected Cyanido Complexes

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The reactions between elemental barium or manganese and tellurium in methylamine under solvothermal conditions at temperatures between 50 and 100 °C yield the tri‐ and ditellurides [Ba(MeNH 2 ) 3 ]Te 3 ( 1 ) and [Mn(MeNH 2 ) 4 Te 2 ] n ( 2 ). The analogous reactions with mixtures of both metals barium and manganese lead additionally to cyanide‐containing species [Mn 2 (MeNH 2 ) 9 (μ‐CN)(Te 2 )] 2 (Te 2 ) ( 3 ) and [Mn 2 (MeNH 2 ) 10 (μ‐CN)] 2 (Te 3 ) 3 · 4MeNH 2 ( 4 ). Under solvothermal conditions in the presence of metallic barium and manganese methylamine partially undergoes dehydrogenation being converted to cyanide ions. In the structure of 1 , Ba 2+ is coordinated by three MeNH 2 ligands and five tellurium atoms of surrounding Te 3 2– anions, which are associated to infinite (Te 3 2– ) n polyanionic chains. 2 is a coordination polymer with Mn(MeNH 2 ) 4 groups connected by Te 2 units to chains [Te–Te–Mn–] n . 3 and 4 are molecular compounds, consisting of cationic dinuclear complexes with almost linear Mn 2+ –CN–Mn 2+ bridges. In the structures 2 – 4 manganese is in octahedral coordination.