Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp(3) )P Pincer Complexes of Iridium.
(2015) In Angewandte Chemie (International edition) 54(32). p.9372-9375- Abstract
- 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.
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/7472597
- author
- Jonasson, Klara LU ; Polukeev, Alexey LU ; Marcos, Rocío ; Ahlquist, Mårten S G and Wendt, Ola LU
- organization
- publishing date
- 2015
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Angewandte Chemie (International edition)
- volume
- 54
- issue
- 32
- pages
- 9372 - 9375
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- pmid:26118858
- wos:000358621500042
- scopus:84938212870
- pmid:26118858
- ISSN
- 1521-3773
- DOI
- 10.1002/anie.201503593
- language
- English
- LU publication?
- yes
- id
- 647f2ed9-98c2-4712-baad-f17ab243225f (old id 7472597)
- date added to LUP
- 2016-04-01 10:08:04
- date last changed
- 2022-04-27 18:53:18
@article{647f2ed9-98c2-4712-baad-f17ab243225f, abstract = {{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 = {{Jonasson, Klara and Polukeev, Alexey and Marcos, Rocío and Ahlquist, Mårten S G and Wendt, Ola}}, issn = {{1521-3773}}, language = {{eng}}, number = {{32}}, pages = {{9372--9375}}, publisher = {{John Wiley & Sons Inc.}}, series = {{Angewandte Chemie (International edition)}}, title = {{Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp(3) )P Pincer Complexes of Iridium.}}, url = {{http://dx.doi.org/10.1002/anie.201503593}}, doi = {{10.1002/anie.201503593}}, volume = {{54}}, year = {{2015}}, }