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

Abstract 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 {Bi 6 } 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 {Bi 6 } unit. This leads to either crown‐shaped cycles for a nominal Bi 6 6− or differently distorted trigonal prisms for compositions close to Bi 6 2− . It was predicted by quantum chemistry that Bi 6 4− 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 [Bi 6 {Zn(hmds)} 2 ] ⋅ 1.5THF ( 1 ), comprising a bimetallic [Bi 6 {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 {Bi 6 } architectures in accordance with the degree of electron‐withdrawal from the polybismuthide core.