A pentamethylcyclopentadienyl
(Cp*) iridium water-oxidation precatalyst
was modified to include a silatrane functional group for covalent
attachment to metal oxide semiconductor surfaces. The heterogenized
catalyst was found to perform electrochemically driven water oxidation
at an overpotential of 462 mV with a turnover number of 304 and turnover
frequency of 0.035 s–1 in a 0.1 M KNO3 electrolyte at pH 5.8. Computational modeling of the experimental
IR spectra suggests that the catalyst retains its Cp* group during
the first hour of catalysis and likely remains monomeric.
Aniline joins the club: A β-diketiminato copper(I) catalyst enables C-H amination of anilines employing low catalyst loadings to preclude oxidation to the diazene ArN=NAr. Electron-poor anilines are particularly resistant towards diazene formation and participate in the amination of strong and unactivated C-H bonds. N-alkyl anilines also take part in C-H amination.
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