Reduction and Rearrangement of a Boron(I) Carbonyl Complex. Issue 6 (11th December 2020)

• Record Type: Journal Article
• Authors: Rang, Maximilian; Fantuzzi, Felipe; Arrowsmith, Merle; Krummenacher, Ivo; Beck, Eva; Witte, Robert; Matler, Alexander; Rempel, Anna; Bischof, Tobias; Radacki, Krzysztof; Engels, Bernd; Braunschweig, Holger
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 6(2021)
• Page Start: 2963
• Page End: 2968
• Publication Date: 2020-12-11
• Subjects: Biradical -- Boron carbonyl complex -- density functional calculations -- Rearrangement -- Reduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202014167
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The one‐electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)‐stabilized arylborylene carbonyl complex yields a dimeric borylketyl radical anion, resulting from an intramolecular aryl migration to the CO carbon atom. Computational analyses support the existence of a [(CAAC)B(CO)Ar] .− radical anion intermediate. Further reduction leads to a highly nucleophilic dianionic (boraneylidene)methanolate. Abstract : The one‐electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)‐stabilized borylene carbonyl complex yields a dimeric borylketyl radical anion, resulting from an intramolecular aryl migration to the CO carbon atom. Computational analyses support the existence of a [(CAAC)B(CO)Ar] .− radical anion intermediate. Further reduction leads to a highly nucleophilic dianionic (boraneylidene)methanolate.