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

Jonasson, Klara LU ; Polukeev, Alexey LU ; Marcos, Rocío ; Ahlquist, Mårten S G and Wendt, Ola LU (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.
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author
; ; ; and
organization
publishing date
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}},
}