Efficient Product Selectivity Modulation of Mn(I) complex-based catalysis by Introduction of alcohol and alkyloxy tethering groups in the secondary coordination sphere
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While the incorporation of pendant Brønsted acid/Lewis base sites in the secondary coordination sphere is a promising and effective strategy to increase the catalytic performance and product selectivity in organometallic catalysis for CO2 reduction, the control of product selectivity still faces a great challenge. Through the formation of pendant alcohol groups in bipyridine, we want to increase product selectivity by creating a Brønsted acid tethering ligand that directly provides proton to metal and creating a Lewis base site through methoxy and ethoxy groups. In the series of photolysis experiments, compared to nontethered case, the asymmetric attachment of tethering ligand to the bpy ligand led to less efficient but more selective formate production with inactivation of CO2-to-CO conversion route during photoreaction. Also, the incorporation of bulky tethering ligands prevented Mn-Mn dimerization.