title: Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH2).
abstract: Two ruthenium complexes containing the tetradentate ligand [1,1'-biisoquinoline]-3,3'-dicarboxylic acid, and 4-picoline or 6-bromoisoquinoline as axial ligands have been prepared. The complexes have been fully characterised and initial studies on their potential to function as molecular water oxidation catalysts have been performed. Both complexes catalyse the oxidation of water in acidic media with CeIVas a stoichiometric chemical oxidant, although turnover numbers and turnover frequencies are modest when compared with the closely related Ru-bda and Ru-pda analogues. Barriers for the water nucleophilic attack and intermolecular coupling pathways were obtained from density functional theory calculations and the crucial influence of the ligand framework in determining the most favourable reaction pathway was elucidated from a combined analysis of the theoretical and experimental results.
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Dominik
authors.initials: D
authors.lastname: Scherrer
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Mauro
authors.initials: M
authors.lastname: Schilling
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Sandra
authors.initials: S
authors.lastname: Luber
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Thomas
authors.initials: T
authors.lastname: Fox
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Bernhard
authors.initials: B
authors.lastname: Spingler
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Roger
authors.initials: R
authors.lastname: Alberto
authors.affiliation: Department of Chemistry, University of Zurich, Zurich, Switzerland. craig.richmond@chem.uzh.ch sandra.luber@chem.uzh.ch.
authors.forename: Craig J
authors.initials: CJ
authors.lastname: Richmond