Abstract
A binuclear Ni complex with N,O donors catalyzes CO2 reduction via its Ni(I) state. The product distribution when H2O is used as a proton source shows similar yields for CO, HCOOH and H2. However, when D2O is used, the product distribution shows a ∼65% selectivity for HCOOH. In situ FTIR indicates that the reaction involves a Ni-COO* and a Ni-CO intermediate. Differences in H/D KIEs on different protonation pathways determine the selectivity of CO2 reduction.
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