The infrared predissociation spectra of the mass-selected electrocatalytic water oxidation intermediate [Ru(tpy)(bpy)(OH)](2+)(H2O)(0-4) are reported. The [Ru(tpy)- (bpy)(OH)(2+) species is generated by passing a solution of [Ru(tpy)(bpy)(H2O)](ClO4)(2) through an electrochemical flow cell held at 1.2 V and is immediately introduced into the gas phase via electrospray ionization (ESI). The micro solvated clusters are formed by reconstructing the water network in a cryogenic ion trap. Details of the hydrogen bonding network in these clusters are revealed by the infrared predissociation spectra in the OH stretch region. This improved method for capturing microsolvated clusters yielded colder complexes with much better resolved IR features than previous studies. The analysis of these spectra, supported by electronic structure calculations and compared to previous results on [Ru(tpy)(bpy)(H2O)](2+)(H2O)(0-4) clusters, reveals the nature of the Ru-OH bond and the effect of hydrogen bonding on facilitating the subsequent oxidation to [Ru(tpy)(bpy)(O)](2+) in the proposed catalytic cycle. Particularly, the hydrogen bonding interaction in [Ru(tpy)(bpy)(OH)](2+)(H2O)(1) is much weaker than that in the corresponding [Ru(tpy)(bpy)(H2O)](2+)(H2O)(1) and thus is less effective at activating the hydroxyl ligand for further oxidation via proton coupled electron transfer (PCET). Furthermore, the results here reveal that the Ru-OH bond, though formally described as an Ru3+/OH- interaction, has more covalent bond character than ionic bond character.