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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
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
external identifiers
  • pmid:26118858
  • wos:000358621500042
  • scopus:84938212870
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
2015-07-17 09:31:47
date last changed
2017-04-30 03:51:28
@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},
  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},
  volume       = {54},
  year         = {2015},
}