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Affecting Charges and Structures of {Bi6} Architectures by 12‐Electron Transition Metal Fragments.

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Název: Affecting Charges and Structures of {Bi6} Architectures by 12‐Electron Transition Metal Fragments.
Autoři: Schmidt, Andreas, Rienmüller, Julia, Weigend, Florian, Dehnen, Stefanie
Zdroj: Angewandte Chemie International Edition; 1/27/2025, Vol. 64 Issue 5, p1-8, 8p
Témata: TRANSITION metals, QUANTUM chemistry, POLYATOMIC molecules, CHEMICAL properties, ELECTRONIC structure
Abstrakt: Molecules based on polyatomic bismuth substructures are currently attracting a lot of attention owing to this heavy and essentially non‐toxic element's uncommon chemical and physical properties, which include unprecedented bonding properties. Hexaatomic {Bi6} substructures that underly more complex cluster structures were recently reported to adopt different structures or exhibit different structural details as a consequence of the charge of the {Bi6} unit. This leads to either crown‐shaped cycles for a nominal Bi66− or differently distorted trigonal prisms for compositions close to Bi62−. It was predicted by quantum chemistry that Bi64− should adopt a distinctly distorted boat‐like shape, yet a corresponding compound has remained elusive. Here, we report a proof of this assumption by the synthesis of [K(crypt‐222)]2[Bi6{Zn(hmds)}2] ⋅ 1.5THF (1), comprising a bimetallic [Bi6{Zn(hmds)}2]2− cluster that fulfills the prediction for the geometric and electronic structure of the missing link (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo‐[8.8.8]hexa‐cosane, hmds=hexamethyldisilazanid). A detailed quantum chemical study shows how the nature of Lewis‐acidic transition metal complexes—in particular, 12‐electron fragments—control and fine‐tune the resulting {Bi6} architectures in accordance with the degree of electron‐withdrawal from the polybismuthide core. [ABSTRACT FROM AUTHOR]
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Databáze: Complementary Index
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Abstrakt:Molecules based on polyatomic bismuth substructures are currently attracting a lot of attention owing to this heavy and essentially non‐toxic element's uncommon chemical and physical properties, which include unprecedented bonding properties. Hexaatomic {Bi6} substructures that underly more complex cluster structures were recently reported to adopt different structures or exhibit different structural details as a consequence of the charge of the {Bi6} unit. This leads to either crown‐shaped cycles for a nominal Bi66− or differently distorted trigonal prisms for compositions close to Bi62−. It was predicted by quantum chemistry that Bi64− should adopt a distinctly distorted boat‐like shape, yet a corresponding compound has remained elusive. Here, we report a proof of this assumption by the synthesis of [K(crypt‐222)]2[Bi6{Zn(hmds)}2] ⋅ 1.5THF (1), comprising a bimetallic [Bi6{Zn(hmds)}2]2− cluster that fulfills the prediction for the geometric and electronic structure of the missing link (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo‐[8.8.8]hexa‐cosane, hmds=hexamethyldisilazanid). A detailed quantum chemical study shows how the nature of Lewis‐acidic transition metal complexes—in particular, 12‐electron fragments—control and fine‐tune the resulting {Bi6} architectures in accordance with the degree of electron‐withdrawal from the polybismuthide core. [ABSTRACT FROM AUTHOR]
ISSN:14337851
DOI:10.1002/anie.202422500