Dinuclear Manganese(II) Complexes with Bridging Selenidodiarsenate Anions [As2Se4]4−, [As2Se5]4− and [As2Se6]2−

Solvothermal reaction of MnCl₂(amine)] (amine = terpy and tren) with elemental As and Se at a 1:1:2 molar ratio in H₂O/tren (10:1) affords the dimanganese(II) complexes {Mn(terpy)}₂(μ‐As₂Se₄)] ( 1 ) and {Mn(tren)}₂(μ‐As₂Se₅)] ( 2 ) respectively. The tetradentate As₂Se₄]^4? bridging ligands in 1 contain a central As–As bond and exhibit approximately C_2h symmetry. Pairs of gauche sited Se atoms participate in five‐membered As₂Se₂Mn chelate rings. In contrast, two AsSe₃ pyramids share a common corner in the As₂Se₅]^4? ligands of 2 and each coordinates an Mn(tren)]²⁺ fragment through a single terminal Se atom. Such dinuclear complexes are linked into tetranuclear moieties through weak Se···Mn interactions of length 3.026(3) Å involving one of these terminal Se atoms. At a 1:3:6 molar ratio, solvothermal reaction of MnCl₂(tren)] with As and Se leads to formation of a second dinuclear complex {Mn(tren)}₂(μ‐As₂Se₆)₂] ( 3 ), which contains two bridging bidentate As₂Se₆]^2? ligands. These are cyclic with an As₂Se₄ ring and can be regarded as being derived from As₂Se₅]^4? anions by formation of two Se‐Se bonds to an additional Se atom.