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Oxidation-induced C-H bond activation in iridium pincer complexes

Polukeev, Alexey V. LU and Tasić, Magdalena LU (2023) In Dalton Transactions 52(22). p.7701-7708
Abstract

Dehydrogenation reactions that produce molecular hydrogen are thermodynamically unfavourable. Desired is to couple them with a green driving force, such as oxidation with oxygen or an electric current. This, in turn, requires understanding of the catalyst's redox properties. Here we report oxidation of the iridium pincer complexes (POCOP)IrHCl (POCOP = 2,6-(tBu2PO)2C6H3; 1a) and (PCP)IrHCl (PCP = 2,6-(tBu2PCH2)2C6H3; 1c) that induced intramolecular C-H activation, followed by the formation of complexes with a cyclometallated tert-butyl group. Based on an electrochemical study and DFT calculations, we propose a... (More)

Dehydrogenation reactions that produce molecular hydrogen are thermodynamically unfavourable. Desired is to couple them with a green driving force, such as oxidation with oxygen or an electric current. This, in turn, requires understanding of the catalyst's redox properties. Here we report oxidation of the iridium pincer complexes (POCOP)IrHCl (POCOP = 2,6-(tBu2PO)2C6H3; 1a) and (PCP)IrHCl (PCP = 2,6-(tBu2PCH2)2C6H3; 1c) that induced intramolecular C-H activation, followed by the formation of complexes with a cyclometallated tert-butyl group. Based on an electrochemical study and DFT calculations, we propose a mechanism that involves H+ loss from hydrochlorides 1a and 1c to give a highly reactive (pincer)IrCl+ compound.

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author
and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
52
issue
22
pages
8 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:37203596
  • scopus:85160448886
ISSN
1477-9226
DOI
10.1039/d3dt00903c
language
English
LU publication?
yes
id
1ec88690-e205-455b-b1f5-a9410b4c00da
date added to LUP
2023-08-24 14:33:33
date last changed
2024-04-20 01:36:01
@article{1ec88690-e205-455b-b1f5-a9410b4c00da,
  abstract     = {{<p>Dehydrogenation reactions that produce molecular hydrogen are thermodynamically unfavourable. Desired is to couple them with a green driving force, such as oxidation with oxygen or an electric current. This, in turn, requires understanding of the catalyst's redox properties. Here we report oxidation of the iridium pincer complexes (POCOP)IrHCl (POCOP = 2,6-(<sup>t</sup>Bu<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; 1a) and (PCP)IrHCl (PCP = 2,6-(<sup>t</sup>Bu<sub>2</sub>PCH<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; 1c) that induced intramolecular C-H activation, followed by the formation of complexes with a cyclometallated tert-butyl group. Based on an electrochemical study and DFT calculations, we propose a mechanism that involves H<sup>+</sup> loss from hydrochlorides 1a and 1c to give a highly reactive (pincer)IrCl<sup>+</sup> compound.</p>}},
  author       = {{Polukeev, Alexey V. and Tasić, Magdalena}},
  issn         = {{1477-9226}},
  language     = {{eng}},
  month        = {{05}},
  number       = {{22}},
  pages        = {{7701--7708}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Oxidation-induced C-H bond activation in iridium pincer complexes}},
  url          = {{http://dx.doi.org/10.1039/d3dt00903c}},
  doi          = {{10.1039/d3dt00903c}},
  volume       = {{52}},
  year         = {{2023}},
}