Copper-oxygen adducts: new trends in characterization and properties towards C-H activation.

This review summarizes the latest discoveries in the field of C-H activation by copper monoxygenases and more particularly by their bioinspired systems. This work first describes the recent background on copper-containing enzymes along with additional interpretations about the nature of the active copper-oxygen intermediates. It then focuses on relevant examples of bioinorganic synthetic copper-oxygen intermediates according to their nuclearity (mono to polynuclear). This includes a detailed description of the spectroscopic features of these adducts as well as their reactivity towards the oxidation of recalcitrant Csp3 -H bonds. The last part is devoted to the significant expansion of heterogeneous catalytic systems based on copper-oxygen cores (i.e. within zeolite frameworks).

Insights into non-covalent interactions in dicopper(II,II) complexes bearing a naphthyridine scaffold: anion-dictated electrochemistry.

A family of bis(µ-hydroxido)dicopper(II,II) complexes bearing a naphthyridine-based scaffold has been synthesized and characterized. Cyclic voltammetry reveals that the nature of the anions present in the complexes plays a pivotal role in their electrochemical properties. X-ray diffraction, spectroscopic and electrochemical analysis data support the formation of intimate ion pairs by non-covalent interactions driving to a ca. 270 mV difference for the potential required to monooxidize the CuIICuII species.

Ruthenium Nanoparticles for Catalytic Water Splitting.

Both global warming and limited fossil resources make the transition from fossil to solar fuels an urgent matter. In this regard, the splitting of water activated by sunlight is a sustainable and carbon-free new energy conversion scheme able to produce efficient technological devices. The availability of appropriate catalysts is essential for the proper kinetics of the two key processes involved, namely, the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). During the last decade, ruthenium nanoparticle derivatives have emerged as true potential substitutes for the state-of-the-art platinum and iridium oxide species for the HER and OER, respectively. Thus, after a summary of the most common methods for catalyst benchmarking, this review covers the most significant developments of ruthenium-based nanoparticles used as catalysts for the water-splitting process. Furthermore, the key factors that govern the catalytic performance of these nanocatalysts are discussed in view of future research directions.

Dissimilar catalytic behavior of molecular or colloidal palladium systems with a new NHC ligand.

In this work, we describe the synthesis of a new N-heterocyclic carbene (NHC) ligand, derived from a hybrid pyrazole-imidazolium scaffold, namely 1-[2-(3,5-dimethylpyrazol-1-yl)ethyl]-3-((S)-1-phenylethyl)-3H-imidazol-2-ylidene (L). This ligand has been used as a stabilizer for the organometallic synthesis of palladium(0) nanoparticles (Pd NPs). L presents a better stabilizing effect than its pre-carbenic HLCl counterpart, allowing the formation of isolated Pd NPs while HLCl yields aggregated ones. Additionally, molecular Pd(ii) coordination compounds of L and HLCl were synthesized and characterized to better understand the coordination modes of these ligands. Both molecular and colloidal Pd systems have been further tested in catalytic C-C coupling processes. Three different types of reactions have been observed depending on the catalytic system: (i) the Suzuki-Miyaura reaction takes place with Pd molecular complexes; (ii) a secondary reaction, the dehalogenation of the substrate, is always detected and (iii) the C-C homocoupling between two molecules of bromoarenes is observed with colloidal catalysts.

Ruthenium complexes with chiral bis-pinene ligands: an array of subtle structural diversity.

A new chiral derivative of the N,N-bis(2-pyridylmethyl)ethylamine (bpea) ligand, Me-pinene[5,6]bpea [(-)-L1], has been prepared from a new aldehyde building block [Me-pinene-aldehyde, (-)-4] arising from the monoterpene chiral pool. The tridentate (-)-L1 ligand has been employed to prepare a new set of Ru-Cl complexes in combination with didentate 2,2'-bipyridine (bpy) with the general formula [RuCl((-)-L1)(bpy)](+). These complexes have been characterized in solution by cyclic voltammetry, UV-vis, and 1D and 2D NMR spectroscopy. Isomeric mixtures of trans,fac-C1a and anti,mer-C1c compounds are formed when (-)-L1 is reacted with a [Ru(bpy)(MeOH)Cl3] precursor. Density functional theory calculations of all of the potential isomers of this reaction have been performed in order to interpret the experimental results in terms of electronic and steric effects and also to unravel the observed isomerization pathway between anti,mer-C1c and trans,fac-C1a.