Reduction of Quinones by NADH Catalyzed by Organoiridium Complexes

One electron at a time: Half‐sandwich organometallic cyclopentadienyl–IrIII complexes containing N,N‐chelated ligands can catalyze the reduction of quinones (Q), such as vitamin K3, to semiquinones (Q.−) by coenzyme NADH (see picture). DFT calculations suggest that the mechanism involves hydride tra...

Full description

Saved in:
Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 52; no. 15; pp. 4194 - 4197
Main Authors Liu, Zhe, Deeth, Robert J., Butler, Jennifer S., Habtemariam, Abraha, Newton, Mark E., Sadler, Peter J.
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 08.04.2013
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Catalysis
Communications
hydride transfer
Hydrides
iridium
Iridium - chemistry
Ligands
Mathematical analysis
Metalorganic compounds
Molecular Structure
NAD - chemistry
NADH
Organometallic Compounds - chemistry
Oxidation-Reduction
Quinones
Quinones - chemistry
radical reactions
Reduction
Valence
Online AccessGet full text

Cover

More Information
Summary:One electron at a time: Half‐sandwich organometallic cyclopentadienyl–IrIII complexes containing N,N‐chelated ligands can catalyze the reduction of quinones (Q), such as vitamin K3, to semiquinones (Q.−) by coenzyme NADH (see picture). DFT calculations suggest that the mechanism involves hydride transfer followed by two one‐electron transfers and the unusual IrII oxidation state as a key transient intermediate.
Bibliography:We thank the ERC (Award 247450 to P.J.S.), members of COST Action CM1105 for stimulating discussions, and the Magnetic Resonance Centre (Warwick University) for EPR support.
Funded Access
ArticleID:ANIE201300747
ark:/67375/WNG-XJFJP26P-N
ERC
COST Action
istex:99FC9AED73C74D8FDD2F4757AE98D986D00A63D0
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 14
content type line 23
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/anie.201300747.
Re-use of this article is permitted in accordance with the Terms and Conditions set out at http://angewandte.org/open.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201300747