Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand
(2023) In European Journal of Inorganic Chemistry 26(31).- Abstract
Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl (1 a) and (POC)(COD)IrHCl (1 b), from which complexes (POC)(L)IrHCl where L=PPh3 (1 c), bipyridine (1 d) and [2,2′-bipyridine]-6,6′-diol (1 e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to... (More)
Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl (1 a) and (POC)(COD)IrHCl (1 b), from which complexes (POC)(L)IrHCl where L=PPh3 (1 c), bipyridine (1 d) and [2,2′-bipyridine]-6,6′-diol (1 e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to dimeric complex [(POC)(bipy-diol−)IrH]2 (3) that could explain the low activity of 1 e. DFT studies provided insight into POC-H vs POCOP-H metalation mechanism.
(Less)
- author
- Polukeev, Alexey V. LU
- organization
- publishing date
- 2023-11
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- acceptorless dehydrogenation, alcohols, bidentate ligands, cyclometalation, iridium
- in
- European Journal of Inorganic Chemistry
- volume
- 26
- issue
- 31
- article number
- e202300351
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- scopus:85170384691
- ISSN
- 1434-1948
- DOI
- 10.1002/ejic.202300351
- language
- English
- LU publication?
- yes
- id
- e7897df7-d3c5-4e22-8f34-d1aad758929d
- date added to LUP
- 2024-01-12 14:51:23
- date last changed
- 2024-01-12 14:53:10
@article{e7897df7-d3c5-4e22-8f34-d1aad758929d,
abstract = {{<p>Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]<sub>2</sub> proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl (1 a) and (POC)(COD)IrHCl (1 b), from which complexes (POC)(L)IrHCl where L=PPh<sub>3</sub> (1 c), bipyridine (1 d) and [2,2′-bipyridine]-6,6′-diol (1 e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to dimeric complex [(POC)(bipy-diol−)IrH]<sub>2</sub> (3) that could explain the low activity of 1 e. DFT studies provided insight into POC-H vs POCOP-H metalation mechanism.</p>}},
author = {{Polukeev, Alexey V.}},
issn = {{1434-1948}},
keywords = {{acceptorless dehydrogenation; alcohols; bidentate ligands; cyclometalation; iridium}},
language = {{eng}},
number = {{31}},
publisher = {{John Wiley & Sons Inc.}},
series = {{European Journal of Inorganic Chemistry}},
title = {{Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand}},
url = {{http://dx.doi.org/10.1002/ejic.202300351}},
doi = {{10.1002/ejic.202300351}},
volume = {{26}},
year = {{2023}},
}