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.