Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

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.