Our work on the mechanism of hydrosilylation of enolizable imines catalyzed by Ir(III) metalacycles reached the cover in Catalysis Science & Technology! The hydrosilylation of enolizable imines using iridacycle catalysts has been investigated using a family of half-sandwich iridium(III) complexes. Several pitfalls had been detected when using standard procedures, and the use of in situ NMR spectroscopy appeared decisive to assess the actual reaction pathway. The results obtained clearly demonstrate that iridacycle-catalyzed hydrosilylation of enolizable imines with monohydrosilanes should be described as a domino reaction sequence, analogous to the one described by Oestreich et al. for boron-based Lewis acid catalysts. Equimolecular quantities of amine (b) and N-silylated enamine (c) were formed in the first stage, consuming 0.5 eq. of hydrosilane, which were subsequently converted into N-silylated amine (d) through a consecutive catalytic cycle using an additional 0.5 eq. of hydrosilane. However, when polyhydrosilanes were used as hydrosilylating agents, N-silylated amine (d) was directly obtained as the reaction product, but after a fast initial conversion, the reaction suffered from product inhibition. Additionally, iridacycles were also found to be active in the dehydrocoupling of Et3SiH and amines and in the hydrolysis of hydrosilanes, which can be competitive processes. These findings lead to an intricate mechanistic […]
A collaboration that originated as a CTP-network gave us this nice paper. Congratullations Jonathan! Abstract Cobalt nanoparticles (NPs) have been prepared by hydrogenation of the organometallic complex [Co(eta(3)-C8H13)(eta(4)-C8H12)] in 1-heptanol in the absence of any other stabilizer and then transformed into Co3O4 NPs using mild oxidative reaction conditions. After deposition onto glassy carbon rotating disk electrodes, the electrocatalytic performance of the Co3O4 NPs in water oxidation has been tested in 1M NaOH. The activity has been benchmarked with that of state-of-the-art Co3O4 NPs through electrochemically-active surface area (ECSA) and specific current density measurements. Furthermore, the covalent grafting of photosensitive polypyridyl-based RuII complexes onto the surface of Co3O4 NPs afforded hybrid nanostructured materials able to photo-oxidize water into O-2, while steady-state and time-resolved spectroscopic measurements gave some further insight into kinetics and pertinent reaction steps following excitation. These first-row transition metal oxide hybrid nanocatalysts display better catalytic performance than simple mixtures of non-grafted photosensitizers and Co3O4 NPs, thus evidencing the advantage of the direct coupling between the two entities for the photo-induced water oxidation reaction. (c) 2018 Elsevier Ltd. All rights reserved. Access full text here.