Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3)2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3)2}2

Abstract

AbstractLowering 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 Ge94− and Sn94−. We developed a new strategy for other anions, using low‐coordinate 3d metal complexes as electrophiles. [K(crypt‐222)]+ salts of (TrBi3)2− anions dissolved in situ in Et2O and/or THF when reacted with [Mn(hmds)2]. Work‐up afforded soluble [K(crypt‐222)]+ salts of [{(hmds)2Mn}2(TlBi3)]2− (in 1), [{(hmds)2Mn}2(Bi2)]2− (in 2), and [{(hmds)Mn}4(Bi2)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(SiMe3)2), representing rare cases of Zintl clusters with open‐shell metal atoms. 1 comprises the first coordination compound of the (TlBi3)2− anion, 2 features a diamond‐shaped {Pn2M2} unit, and 3 is a mixed‐valent MnI/MnII compound. The uncommon electronic structures in 1–3 and magnetic coupling were studied by comprehensive DFT calculations.