Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp(3) )P Pincer Complexes of Iridium.

Summary, in English

Despite significant progress in recent years, the cleavage of unstrained C(sp(3) )C(sp(3) ) bonds remains challenging. A CC coupling and cleavage reaction in a PC(sp(3) )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(sp(3) )C(sp(3) ) 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 CC agostic intermediate is presented.

• Author: Klara Jonasson; Alexey Polukeev; Rocío Marcos; Mårten S G Ahlquist; Ola Wendt
• Department/s: Centre for Analysis and Synthesis
• Publishing year: 2015
• Language: English
• Pages: 9372-9375
• Publication/Series: Angewandte Chemie (International edition)
• Volume: 54
• Issue: 32
• Links: http://dx.doi.org/10.1002/anie.201503593
• Document type: Journal article
• Publisher: John Wiley & Sons Inc.
• Topic: Organic Chemistry
• Status: Published
• ISBN/ISSN/Other: ISSN: 1521-3773