Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis.

Inspired by copper-containing enzymes such as galactose oxidase and catechol oxidase, in which distinct coordination environments and nuclearities lead to specific catalytic activities, we summarize here the catalytic properties of dinuclear and mononuclear copper species towards benzyl alcohol oxidation using a multivariate statistical approach. The new dinuclear [Cu(μ-L)(μ-pz)] (1) is compared against the mononuclear [CuLCl] (2), where (L) and (L) are the respective deprotonated forms of 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol, and 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde and (pz) is a pyrazolato bridge. Copper(II) perchlorate (CP) is used as control.

Reactivity and Mechanisms of Photoactivated Heterometallic [Ru Ni ] and [Ru Ni Ru ] Catalysts for Dihydrogen Generation from Water.

Two heterometallic photocatalysts were designed and probed for water reduction. Both [(bpy) Ru Ni (L )](ClO ) (1) and [(bpy) Ru Ni (L ) Ru (bpy) ](ClO ) (2) can generate the low-valent precursor involved in hydride formation prior to dihydrogen generation. However, while the bimetallic [Ru Ni ] (1) requires the presence of an external photosensitizer to trigger catalytic activity, the trimetallic [Ru Ni Ru ] (2) displays significant coupling between the catalytic and light-harvesting units to promote intramolecular multielectron transfer and perform photocatalysis at the Ni center.