Towards Nickel‐Catalysed Olefin Metathesis: A Computational Study of Nickelacyclobutane Fragmentation Reactions
Year: 2025
Type: article
Abstract: A detailed picture of the reactivity of metallacyclobutanes is key to the understanding and development of new reactions relying on these reactive intermediates, including olefin metathesis and cyclopropanation. More than 40 years ago, Miyashita and Grubbs reported experimental studies on the thermal decomposition pathways of a phosphine‐supported nickelacyclobutane (NiCB) suggesting that nickel may be amenable to both cyclopropanation and olefin metathesis. Here we report a computational investigation of this system that shows that cyclopropane reductive elimination is the primary decomposition pathway for monometallic NiCBs, independently of the number of coordinated phosphine ligands. Further calculations suggest that bimetallic species may be responsible for the olefinic products of apparent [2+2] cycloreversion.
Source: Helvetica Chimica Acta
Authors: Olaf L. Kooijman, Marc‐Etienne Moret
Institution: Utrecht University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,030
OpenAlex ID: W4409813268