Reactive Solubilization of Heterometallic Clusters by Treatment of (trbi3)2− Anions (tr=ga, In, Tl) with [Mn{n(sime3)2}2]

Lowering the charge of Zintl anions by (element‐)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge 9 4− and Sn 9 4− . We developed a new strategy for other anions, using low‐coordinate 3d metal complexes as electrophiles. [K(crypt‐222)] + salts of (TrBi 3 ) 2− anions dissolved in situ in Et 2 O and/or THF when reacted with [Mn(hmds) 2 ]. Work‐up afforded soluble [K(crypt‐222)] + salts of [{(hmds) 2 Mn} 2 (TlBi 3 )] 2− (in 1 ), [{(hmds) 2 Mn} 2 (Bi 2 )] 2− (in 2 ), and [{(hmds)Mn} 4 (Bi 2 ) 2 ] 2− (in 3 ) (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe 3 ) 2 ), representing rare cases of Zintl clusters with open‐shell metal atoms. 1 comprises the first coordination compound of the (TlBi 3 ) 2− anion, 2 features a diamond‐shaped {Pn 2 M 2 } unit, and 3 is a mixed‐valent Mn I /Mn II compound. The uncommon electronic structures in 1 – 3 and magnetic coupling were studied by comprehensive DFT calculations.