Send to

Choose Destination
See comment in PubMed Commons below
Inorg Chem. 2010 May 17;49(10):4543-53. doi: 10.1021/ic100075k.

Acid-base mechanism for ruthenium water oxidation catalysts.

Author information

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.


We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<5 kcal/mol) for each rearrangement in the catalytic cycle. In the crucial step of O-O bond formation, a solvent water acts as a Lewis base and attacks a highly oxidized Ru(V)=O. Armed with the structures and energetics of the single-center catalyst, we proceed to consider a representative Ru-dimer which was designed to form O(2) via coupling between the two centers. We discover a mechanism that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer. This acid-base mechanism suggests a new set of strategies for the rational design of multicenter catalysts: rather than coordinating the relative orientations of the subunits, one can focus on coordinating solvation-shell water molecules or tuning redox potentials.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Support Center