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

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 Ge₉ ^4- and Sn₉ ^4- . 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 Et₂ O and/or THF when reacted with [Mn(hmds)₂ ]. Work-up afforded soluble [K(crypt-222)]⁺ salts of [{(hmds)₂ Mn}₂ (TlBi₃ )]^2- (in 1), [{(hmds)₂ Mn}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 {Pn₂ M₂ } 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.

SUBMITTER: Rienmuller J 

PROVIDER: S-EPMC9825972 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature