Oxidation, Coordination, and Nickel‐Mediated Deconstruction of a Highly Electron‐Rich Diboron Analogue of 1,3,5‐Hexatriene

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 C2B2C2 chain. While this divinyldiborene coordinates to copper(I) and...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-09, Vol.59 (36), p.15717-15725
Main Authors: Hermann, Alexander, Fantuzzi, Felipe, Arrowsmith, Merle, Zorn, Theresa, Krummenacher, Ivo, Ritschel, Benedikt, Radacki, Krzysztof, Engels, Bernd, Braunschweig, Holger
Format: Article
Language:English
Subjects:
carbenes
Conjugation
density-functional calculations
Nickel
Oxidation
Platinum
rearrangements
structure elucidation
Twisting
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 C2B2C2 chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η2‐B2 and η4‐C2B2 fashion, respectively, it undergoes a complex rearrangement to an η4‐1,3‐diborete upon complexation with nickel(0). A complex twist: A highly electron‐richN‐heterocyclic carbene stabilized 1,2‐divinyldiborene, which displays no delocalized π conjugation because of twisting of the C2B2C2 chain, coordinates to CuI and Pt0 in an η2‐B2 and η4‐C2B2 mode, respectively, while undergoing a complex rearrangement to an η4‐1,3‐diborete upon complexation with Ni0.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202006131