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This study provides evidence that catalytic water oxidation driven by CAN provides access to reaction pathways that diverge from the prevailing ¡°acid base¡± mechanism for single-site catalysts. The preference for each of these pathways is
dependent on reaction conditions and electron density at the metal site. The position of the RDS is shown to be sensitive to electron density at the Ru center and shows that higher catalytic activity is attained when the [RuV OO]2 is made accessible(i.e., RDS is kO2¡ä rather than kO2). However, too much density at the metal site can compromise the critical bond formation step, thus highlighting the inherent limitation for achieving high catalytic rates with catalysts of this type. This study also demonstrates that a minor auxiliary reaction pathway may be operative that enables the incorporation of an O-atom from a source other than water (e.g., CAN) into the dioxygen product. These findings provide important insight into the design and study of homogeneous water oxidation catalysts.
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