Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent‐Induced Dissociation Effects

Rare examples of heavier alkali metal manganates [{(AM)Mn(CH(2)SiMe(3))(N(‘Ar))(2)}(∞)] (AM=K, Rb, or Cs) [N(‘Ar)=N(SiMe(3))(Dipp), where Dipp=2,6‐iPr(2)‐C(6)H(3)] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig‐zag chains propagated by AM⋅⋅⋅π‐arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li ‐ Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s‐block metal amides, six new derivatives ([{AM(N(‘Ar))}(∞)], [{AM(N(‘Ar))⋅TMEDA}(∞)], and [{AM(N(‘Ar))⋅PMDETA}(∞)] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et(2)O)(2)Na(( n )Bu)Mn[(N(‘Ar))(2)], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium.