Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi ₃ ) ²⁻ Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe ₃ ) ₂ } ₂ ]

Lowering the charge of Zintl anions by (element-)organic substituents allows their use as sources (semi)metal nanostructures in common organic solvents, realized for group 15 or Ge94− and Sn94−. We developed a new strategy other anions, using low-coordinate 3d metal complexes electrophiles. [K(crypt-222)]+ salts (TrBi3)2− dissolved situ Et2O and/or THF when reacted with [Mn(hmds)2]. Work-up afforded soluble [{(hmds)2Mn}2(TlBi3)]2− (in 1), [{(hmds)2Mn}2(Bi2)]2− 2), [{(hmds)Mn}4(Bi2)2]2− 3) (crypt-222=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe3)2), representing rare cases clusters open-shell atoms. 1 comprises first coordination compound (TlBi3)2− anion, 2 features diamond-shaped {Pn2M2} unit, 3 is mixed-valent MnI/MnII compound. The uncommon electronic structures 1–3 magnetic coupling were studied comprehensive DFT calculations.