Combinatorial approach to chiral tris-ligated carbophilic platinum complexes: application to asymmetric catalysis.

A straightforward methodology for the synthesis of libraries of chiral tris-ligated cationic platinum complexes and their in situ evaluation as asymmetric carbophilic catalysts in a model domino hydroarylation/cyclization reaction of a 1,6-enyne was developed. A catalyst-generation process based on a combination of a monodentate and a bidentate phosphorus ligand allowed the formation of 108 chiral complexes. One-pot screening of the stereoinduction obtained with this library in a test domino addition/cyclization reaction validated this approach and stressed the key role played by the monodentate ligand partner in obtaining high enantioselectivities.

A noble-metal-free system for photocatalytic hydrogen production from water.

A series of heteroleptic copper(I) complexes with bidentate PP and NN chelate ligands was prepared and successfully applied as photosensitizers in the light-driven production of hydrogen, by using [Fe3(CO)12] as a water-reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble-metal-free systems.

Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide.

Hydrogen produced from renewable resources is a promising potential source of clean energy. With the help of low-temperature proton-exchange membrane fuel cells, molecular hydrogen can be converted efficiently to produce electricity. The implementation of sustainable hydrogen production and subsequent hydrogen conversion to energy is called "hydrogen economy".

Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system.

Of noble descent: a fully noble-metal-free system for the photocatalytic reduction of water at room temperature has been developed. This system consists of Cu(I) complexes as photosensitizers and [Fe(3)(CO)(12)] as the water-reduction catalyst. The novel Cu-based photosensitizers are relatively inexpensive, readily available from commercial sources, and stable to ambient conditions, thus making them an attractive alternative to the widely used noble-metal based systems.

Water oxidation with molecularly defined iridium complexes: insights into homogeneous versus heterogeneous catalysis.

Molecularly defined Ir complexes and different samples of supported IrO(2) nanoparticles have been tested and compared in the catalytic water oxidation with cerium ammonium nitrate (CAN) as the oxidant. By comparing the activity of nano-scaled supported IrO(2) particles to the one of organometallic complexes it is shown that the overall activity of the homogeneous Ir precursors is defined by both the formation of the homogeneous active species and its conversion to Ir(IV)-oxo nanoparticles. In the first phase of the reaction the activity is dominated by the homogeneous active species.