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Updated: Dec 30, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Mass Spectrometric and Vibrational Characterization of Reaction Intermediates in [Ru(bpy)(tpy)(H2 O)]2+ Catalyzed
Jonathan M Voss1, Erin M Duffy1, Brett M Marsh1
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA), E-mail: Etienne Garand.
Abstract:
Mass spectrometry coupled with an in-line electrochemical electrospray ionization source is used to capture some of the reaction intermediates formed in the [Ru(bpy)(tpy)(H2 O)]2+ (bpy=2,2'-bipyridine, tpy=2,2':6',2"-terpyridine) catalyzed water oxidation reaction. By controlling the applied electrochemical potential, we identified the parent complex, as well as the first two oxidation complexes, identified as [Ru(bpy)(tpy)(OH)]2+ and [Ru(bpy)(tpy)(O)]2+ . The structures of the parent and first oxidation complexes are probed directly in the mass spectrometer by using infrared predissociation spectroscopy of D2 -tagged ions. Comparisons between experimental vibrational spectra and density functional theory calculations confirmed the identity and structure of these two complexes. Moreover, the frequency of the O-H stretching mode in [Ru(bpy)(tpy)(OH)]2+ shows that this complex features a Ru-OH interaction that is more covalent than ionic.
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