Inorganic Chemistry, Vol.56, No.17, 10235-10246, 2017
Mechanistic Insight into Reversible Core Structural Changes of Dinuclear mu-Hydroxoruthenium(II) Complexes with a 2,8-Di-2-pyridyl-1,9,10-anthyridine Backbone Prior to Water Oxidation Catalysis
proximal,proximal-(p,p)-[Ru-2(II)(tpy)(2)LXY](n+) (tpy = 2,2';6',2 ''-terpyridine, L = 5-phenyl-2,8-di-2-pyridyl-1,9,10-anthyridine, and X and Y = other coordination sites) yields the structurally and functionally unusual Ru-II(mu-OH)Ru-II core, which is capable of catalyzing water oxidation with key water insertion to the core (Inorg. Chem. 2015, 54, 7627). Herein, we studied a sequence of bridging-ligand substitution among p,p-[Ru-2(tpy)(2)L(mu-Cl)](3+) (RU2(mu-Cl)), p,p-[Ru-2(tpy)(2)L(mu-OH)](3+) (Ru-2(mu-OH)), p,p-[Ru-2(tpy)(2)L-(OH)(OH2)](3+) (Ru-2(OH)(OH2)), and p,p-[Ru-2(tpy)(2)L-(OH)(2)](2+) (Ru-2(OH)(2)) in aqueous solution. Ru-2(mu-Cl) converted slowly (10(-4) s(-1)) to Ru-2(mu-OH), and further Ru-2(mu-OH) converted very slowly (10(-6) s(-1)) to Ru-2(OH)-(OH2) by the insertion of water to reach equilibrium at pH 8.5-12.3. On the basis of density functional theory (DFT) calculations, Ru-2(OH)(OH2) was predicted to be thermodynamically stable by 13.3 kJ mol(-1) in water compared to Ru-2(mu-OH) because of the specially stabilized core structure by multiple hydrogen-bonding interactions involving aquo, hydroxo, and L backbone ligands. The observed rate from Ru-2(mu-OH) to Ru-2(OH)(2) by the insertion of an OH- ion increased linearly with an increase in the OH- concentration from 10 to 100 mM. The water insertion to the core is very slow (similar to 10(-6) s(-1)) in aqueous solution at pH 8.5-12.3, whereas the insertion of OH- ions is accelerated (10(-5)-10(-4) s(-1)) above pH 13.4 by 2 orders of magnitude. The kinetic data including activation parameters suggest that the associative mechanism for the insertion of water to the Ru-II(mu-OH)Ru-II core of Ru-2(mu-OH) at pH 8.5-12.3 alters the interchange mechanism for the insertion of an OH- ion to the core above pH 13.4 because of relatively stronger nucleophilic attack of OH- ions. The hypothesized p,p-[Ru-2(tpy)(2)L(mu-OH2)](4+) and p,p-[Ru-2(tpy)(2)L(OH2)(2)](4+) formed by protonation from Ru-2(mu-OH) and Ru-2(OH)(OH2) were predicted to be unstable by 71.3 and 112.4 kJ mol(-1) compared to Ru-2(mu-OH) and Ru-2(OH)(OH2), respectively. The reverse reactions of Ru-2(mu-OH), Ru-2(OH)(OH2), and Ru-2(OH)(2) to Ru-2(mu-Cl) below pH 5 could be caused by lowering the core charge by protonation of the mu-OH- or OH- ligand.