Mechanistic Studies on the Reversible Hydrogenation of Carbon Dioxide Catalyzed by an Ir-PNP Complex

The PNP-ligated iridium(III) trihydride complex 1 exhibited the highest catalytic activity for hydrogenation of carbon dioxide in aqueous KOH. The catalytic hydrogenation can be tuned to be a reversible process with the same catalyst at the expense of the activity, when triethanolamine was used as a...

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Bibliographic Details
Published in:Organometallics 2011-12, Vol.30 (24), p.6742-6750
Main Authors: Tanaka, Ryo, Yamashita, Makoto, Chung, Lung Wa, Morokuma, Keiji, Nozaki, Kyoko
Format: Article
Language:English
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Summary:The PNP-ligated iridium(III) trihydride complex 1 exhibited the highest catalytic activity for hydrogenation of carbon dioxide in aqueous KOH. The catalytic hydrogenation can be tuned to be a reversible process with the same catalyst at the expense of the activity, when triethanolamine was used as a base. Theoretical studies on the hydrogenation of carbon dioxide using DFT calculations suggested two competing reaction pathways: either the deprotonative dearomatization step or the hydrogenolysis step as the rate-determining step. The results nicely explain our experimental observations that the catalytic cycle is dependent on both the strength of the base and hydrogen pressure.
ISSN:0276-7333
1520-6041
DOI:10.1021/om2010172