NDLI: Long-range metal–ligand bifunctional catalysis: cyclometallated iridium catalysts for the mild and rapid dehydrogenation of formic acid

Content Provider	Royal Society of Chemistry (RSC)
Author	Barnard, Jonathan H. Wang, Chao Berry, Neil G. Xiao, Jianliang
Copyright Year	2013
Abstract	Formic acid (HCO2H) is an important potential hydrogen storage material, which, in the presence of appropriate catalysts can be selectively dehydrogenated to give H2 and CO2. In this work, well defined N^C cyclometallated iridium(III) complexes based on 2-aryl imidazoline ligands are found to be excellent catalysts for the decomposition of HCO2H–NEt3 mixtures to give H2 and CO2 under mild conditions with high turnover frequencies (up to 147 000 h−1 at 40 °C) and essentially no CO formation. The modular structures of these catalysts have allowed for the construction of structure–activity relationships for the complexes, leading to the rational optimisation of the catalyst structure with respect to both the rate of H2 production and catalyst lifetime. In particular, the presence of the remote γ-NH unit in the ligand is shown to be essential for catalytic activity, without which no reaction occurs. Mechanistic studies suggest that the dehydrogenation is rate-limited by the step of hydride protonation, which is made feasible by the γ-NH unit via an unusual form of long-range metal–ligand bifunctional catalysis involving formic acid-assisted proton hopping.
Starting Page	1234
Ending Page	1244
Page Count	11
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	4
Issue Number	3
Journal	Chemical Science
DOI	10.1039/c2sc21923a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Hydrogen storage Ligand Dehydrogenation Hydrogen Imidazoline Hydride Iridium Aryl
Content Type	Text
Resource Type	Article
Subject	Chemistry

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