Efficient Fixation of Carbon Dioxide by Hypervalent Organobismuth Oxide, Hydroxide, and Alkoxide

Abstract

CO2 unter Kontrolle: Atmosphärisches CO2 kann irreversibel durch hypervalente Organobismutoxide und ‐hydroxide gebunden werden, wohingegen ein analoges Alkoxid das Treibhausgas reversibel anlagert (siehe Schema). Die Hypervalenz der Bismutverbindungen spielt bei diesen Reaktionen eine entscheidende Rolle.

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns

“…In contrast to the lanthanide analogues, the Bi 3+ ion is additionally coordinated by only one oxygen atom of the hydroxide anion in an apical position. The Bi-O distance (2.047(7), 2.106(8) Å) is in excellent agreement with the literature data on the compounds with the Bi-OH bonds [ 38 , 39 , 40 ]. The nearest water molecules are at the distance of 2.920(8) and 2.996(8) Å from Bi in the A and B molecules, respectively.…”

Synthesis and Structure of Binuclear O/S‐Bridged Organobismuth Complexes and Their Cooperative Catalytic Effect on CO2 Fixation

“…A typical complex is a binuclear organobismuth oxide (cat. 1 , Scheme ; LBi‐O‐BiL, L=RN(CH 2 C 6 H 4 ) 2 , R= t Bu) that can react with CO 2 to form a bismuth carbonate species 4e. To the best of our knowledge, there is no report on the utilization of binuclear organobismuth complexes as catalysts for the CO 2 transformation to useful chemicals.…”

Highly Efficient and Selective Synthesis of (E)‐α,β‐Unsaturated Ketones by Crossed Condensation of Ketones and Aldehydes Catalyzed by an Air‐Stable Cationic Organobismuth Perfluorooctanesulfonate

“…The BiS(1) distance [2.704 (2) Å] is shorter than that (2.845 Å) of precursor 2 ,15b clearly showing the stronger sulfur‐to‐bismuth coordination in 1 . The BiO(1) distance [2.445 (7) Å] is longer than that of covalent BiO bonds (e.g., BiO bond distances of monomeric diorganobismuth alkoxides range 2.15–2.20 Å),4b,17 indicating that the weakly coordinated water molecule can be replaced by another substrate.…”