Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex. Issue 44 (4th July 2018)

• Record Type: Journal Article
• Authors: Schneck, Felix; Schendzielorz, Florian; Hatami, Nareh; Finger, Markus; Würtele, Christian; Schneider, Sven
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 44(2018)
• Page Start: 14482
• Page End: 14487
• Publication Date: 2018-07-04
• Subjects: CO2 -- hydrogenation -- nickel -- photochemistry -- pincer ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201803396
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The endothermic reverse water‐gas shift reaction (rWGS) for direct CO2 hydrogenation to CO is an attractive approach to carbon utilization. However, direct CO2 hydrogenation with molecular catalysts generally gives formic acid instead of CO as a result of the selectivity of CO2 insertion into M−H bonds. Based on the photochemical inversion of this selectivity, several synthetic pathways are presented for CO selective CO2 reduction with a nickel pincer platform including the first example of a photodriven rWGS cycle at ambient conditions. Abstract : Let there be light : A simple, two‐step photodriven reverse‐water‐gas‐shift (rWGS) cycle at ambient temperature and pressure is reported. The CO2 to CO hydrogenation is mediated by a molecular nickel hydride. The reaction relies on photochemical abnormal CO2 insertion into the Ni−H bond and cooperative, heterolytic H2 ‐activation by the metal and the functional pincer ligand.