The greater reduction in energy gap on complexation for the directly bound triazine species compared to the phenanthroline provides a rationale for the greater increase in experimentally observed reaction rate. Analysis of frontier orbital overlap integrals showed little difference between the directly bound triazine and phenanthroline on complexation, suggesting that the orbital energy differences have the most profound impact on reaction rate. Details of the frontier molecular orbitals and tabulated values are provided in the Supporting Information.