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Updated: Jul 12, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Reactivity of an adsorbed Ru(VI)-oxo complex: oxidation of benzyl alcohol
Brooks J Hornstein1, Dana M Dattelbaum, Jon R Schoonover
1Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
Abstract:
The phosphonated ruthenium complex, [Ru(tpy-PO(3)H(2))(OH(2))(3)](2+) (1) (tpy-PO(3)H(2) = 4'-phosphonato-2,2':6',2' '-terpyridine), was synthesized and attached to glass|ITO or glass|ITO|TiO(2) electrodes. After attachment to the metal oxide surface through the phosphonate linkage, 1 can be oxidized (either chemically or electrochemically) to the reactive Ru(VI)-dioxo complex, glass|ITO|[((HO)(2)OP)tpy)RuVI(O)(2)(OH(2))](2+), which remains attached to the surface. The attached Ru(VI) complex reacts with benzyl alcohol through mechanisms similar to those proposed for the solution analog. More specifically, Ru(VI) is reduced in a stepwise fashion to Ru(IV) and then finally to Ru(II). The reduction of Ru(VI) is accompanied by a rate-limiting insertion to the C-H bond of benzyl alcohol, followed by solvolysis of the aldehyde hydrate. In addition, the surface-bound Ru(VI) acts as an electrooxidation catalyst which carries out approximately 130 (2e(-)) turnovers before deactivation.
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