Reversible α‐Hydrogen and α‐Alkyl Elimination in PC(sp3)P Pincer Complexes of Iridium1. (26th June 2015)

• Record Type: Journal Article
• Authors: Jonasson, Klara J.; Polukeev, Alexey V.; Marcos, Rocío; Ahlquist, Mårten S. G.; Wendt, Ola F.
• Is Part Of: Angewandte Chemie. Volume 127:Number 32(2015)
• Page Start: 9504
• Page End: 9507
• Publication Date: 2015-06-26
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201503593
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Despite significant progress in recent years, the cleavage of unstrained C(sp³)C(sp³) bonds remains challenging. A CC coupling and cleavage reaction in a PC(sp³)P iridium pincer complex is mechanistically studied; the reaction proceeds via the formation of a carbene intermediate and can be described as a competition between α‐hydrogen and α‐alkyl elimination; the latter process was observed experimentally and is an unusual way of C(sp³)C(sp³) bond scission, which has previously not been studied in detail. Mechanistic details that are based upon kinetic studies, activation parameters, and DFT calculations are also discussed. A full characterization of a CC agostic intermediate is presented.</p> </abstract>