Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi<sub>3</sub>)<sup>2−</sup> Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe<sub>3</sub>)<sub>2</sub>}<sub>2</sub>]
Julia Rienmüller, Andreas Schmidt, Nathan J. Yutronkie, Rodolphe Clérac, C. Gunnar Werncke, Florian Weigend, Stefanie Dehnen
Abstract
Abstract 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.