Ligand-Bound CO 2 as a Nonclassical Route toward Efficient Photocatalytic CO 2 Reduction with a Ni N-Confused Porphyrin.

Implementing the synergistic effects between the metal and the ligand has successfully streamlined the energetics for CO 2 activation and gained high catalytic activities, establishing the important breakthroughs in photocatalytic CO 2 reduction. Herein, we describe a Ni(II) N-confused porphyrin complex ( NiNCP ) featuring an acidic N-H group. It is readily deprotonated and exists in an anion form during catalysis. Owing to this functional site, NiNCP gave rise to an outstanding turnover number (TON) as high as 217,000 with a 98% selectivity for CO 2 reduction to CO, while the parent Ni(II) porphyrin ( NiTPP ) was found to be nearly inactive. Our mechanistic analysis revealed a nonclassical reaction pattern where CO 2 was effectively activated via the attack of the Lewis-basic ligand. The resulting ligand-bound CO 2 adduct could be further reduced to produce CO. This new metal-ligand synergistic effect is anticipated to inspire the design of highly active catalysts for small molecule activations.