Iridium Dihydroxybipyridine Complexes Show That Ligand Deprotonation Dramatically Speeds Rates of Catalytic Water Oxidation

We report highly active iridium precatalysts, Cp*Ir(N,N)ClCl (1-4), for water oxidation that are supported by recently designed dihydroxybipyridine (dhbp) ligands. These ligands can readily be deprotonated in situ to alter the electronic properties at the metal; thus, these catalyst precursors have switchable properties that are pH-dependent. The pKa values in water of the iridium complexes are 4.6(1) and 4.4(2) with (N,N) = 6,6'-dhbp and 4,4'-dhbp, respectively, as measured by UV-vis spectroscopy. For homogeneous water oxidation catalysis, the sacrificial oxidant NaIO4 was found to be superior (relative to CAN) and allowed for catalysis to occur at higher pH values. With NaIO4 as the oxidant at pH 5.6, water oxidation occurred most rapidly with (N,N) = 4,4'-dhbp, and activity decreased in the order 4,4'-dhbp (3) > 6,6'-dhbp (2) ≫ 4,4'-dimethoxybipyridine (4) > bipy (1). Furthermore, initial rate studies at pH 3-6 showed that the rate enhancement with dhbp complexes at high pH is due to ligand deprotonation rather than the pH alone accelerating water oxidation. Thus, the protic groups in dhbp improve the catalytic activity by tuning the complexes' electronic properties upon deprotonation. Mechanistic studies show that the rate law is first-order in an iridium precatalyst, and dynamic light scattering studies indicate that catalysis appears to be homogeneous. It appears that a higher pH facilitates oxidation of precatalysts 2 and 3 and their B(Ar(F))4(-) salt analogues 5 and 6. Both 2 and 5 were crystallographically characterized.