Oxidation-induced C-H bond activation in iridium pincer complexes
(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
- Polukeev, Alexey V. LU and Tasić, Magdalena LU
- organization
- publishing date
- 2023-05-09
- 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}}, }