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> ] - Archive ouverte HAL Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2022

Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi 3 ) 2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe 3 ) 2 } 2 ]

(1) , (2) , (3) , (3) , (4) , (5) , (6)
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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 diamondshaped {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.
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hal-03821174 , version 1 (19-10-2022)

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Julia Rienmüller, Andreas Schmidt, Nathan J Yutronkie, Rodolphe Clérac, C Gunnar Werncke, et al.. Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi 3 ) 2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe 3 ) 2 } 2 ]. Angewandte Chemie International Edition, 2022, 61 (42), ⟨10.1002/anie.202210683⟩. ⟨hal-03821174⟩

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