Oxidation, Coordination, and Nickel‐Mediated Deconstruction of a Highly Electron‐Rich Diboron Analogue of 1, 3, 5‐Hexatriene. (1st July 2020)

• Record Type: Journal Article
• Authors: Hermann, Alexander; Fantuzzi, Felipe; Arrowsmith, Merle; Zorn, Theresa; Krummenacher, Ivo; Ritschel, Benedikt; Radacki, Krzysztof; Engels, Bernd; Braunschweig, Holger
• Is Part Of: Angewandte Chemie. Volume 132:Number 36(2020)
• Page Start: 15847
• Page End: 15855
• Publication Date: 2020-07-01
• Subjects: carbenes -- conjugation -- density-functional calculations -- rearrangements -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202006131
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The reductive coupling of an N‐heterocyclic carbene (NHC) stabilized (dibromo)vinylborane yields a 1, 2‐divinyldiborene, which, although isoelectronic to a 1, 3, 5‐triene, displays no extended π conjugation because of twisting of the C2 B2 C2 chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η 2 ‐B2 and η 4 ‐C2 B2 fashion, respectively, it undergoes a complex rearrangement to an η 4 ‐1, 3‐diborete upon complexation with nickel(0). Abstract : A complex twist : A highly electron‐rich N‐heterocyclic carbene stabilized 1, 2‐divinyldiborene, which displays no delocalized π conjugation because of twisting of the C2 B2 C2 chain, coordinates to Cu I and Pt 0 in an η 2 ‐B2 and η 4 ‐C2 B2 mode, respectively, while undergoing a complex rearrangement to an η 4 ‐1, 3‐diborete upon complexation with Ni 0 .