A facile surface-amide coupling method was examined to attach dye and catalyst molecules to silatrane-decorated NiO electrodes. Using this method, electrodes with a push-pull dye were assembled, and characterized by photoelectrochemistry and transient absorption spectroscopy. The dye-sensitized electrodes exhibited hole injection into NiO and good photoelectrochemical stability in water, highlighting the stability of the silatrane anchoring group and the amide linkage. The amide coupling protocol was further applied to electrodes that contain additional proton reduction nickel catalysts for use in photocathode architectures. Evidence for catalyst reduction was observed during photoelectrochemical measurements and via fs-transient absorption spectroscopy demonstrating the possibility for application in photocathodes.

The effect of the carboxylate used in a concerted metalation−deprotonation reaction is probed and shows a direct correlation of pK a to observed rate up to a pK a of 4.3, where the rate drops off at higher pK a . The rate of the C−H activation of 2-(4-methoxyphenyl)pyridine with [Cp*RhCl 2 ] 2 and carboxylate follows first-order kinetics in the active metal species, Cp*RhCl(κ 2 -OAc), and zero-order kinetics in substrate when in a 1:1 ratio. There is a first-order dependence on substrate observed when excess substrate is present. The evaluation of the mechanism using kinetic studies allowed for a mechanistic proposal in which a second Ph′Py coordinates prior to the rate-determining C−H activation.

Reaction of Pt(dippe)(NBE)2 (NBE = norbornene) with a variety of esters leads to a product in which the less reactive C–O bond is cleaved to give Pt(dippe)(O2CR)(R′). A further disproportionation reaction occurs to eliminate R′2 and produce Pt(dippe)(O2CR)2. Details of the mechanisms of these reactions are explored.

The influence of a biologically inspired second and outer coordination sphere on Rh-bis(diphosphine) CO2 hydrogenation catalysts was explored.