Palladium(II) complexes containing phosphine donor ligands derived from naphthyl(diphenyl)phosphine were synthesized and characterized by NMR and elemental analysis. The complexes were studied as catalyst precursors in the methoxycarbonylation reaction of several aromatic and aliphatic olefins under mild conditions. The catalysts reported high chemoselectivities (over 96%) and regioselectivities between 44% and 93% for different olefins. The best results were obtained over a styrene substrate with 97% of conversion after 6 h of reaction, with high regioselectivity (93%). Kinetic studies permitted the determination of the rate law (v = k [substrate]1.21±0.02 [catalyst]0.94±0.11 [acid]0.52±0.03 [MeOH]0.53±0.05 [CO]0.65±0.03) for methoxycarbonylation of styrene. Copyright © 2014 John Wiley & Sons, Ltd.

Two ruthenium (II) complexes containing heterobidentated phosphorous–nitrogen ligands were studied as homogeneous catalysts in the hydrogenation of furfural, a key step in the transformation of biomass to biofuels or renewable chemicals. The catalysts exhibited high percentages of conversion towards the formation of furfuryl alcohol. The studied ruthenium (II) complexes are able to maintain their catalytic activities in substrate/catalyst ratios ranging from 1000/1 to 6000/1. The reaction is sensitive to hydrogen pressure and the substrate concentration. The maximum conversion is achieved at a pressure of 40 bar and a substrate/catalyst ratio of 3000/1 (TOF 3000 h−1). In situ 1H‐NMR (proton nuclear magnetic resonance) analysis suggests that the presence of a phosphorous–nitrogen ligand improves the catalytic activity of the complex by stabilizing the intermediate ruthenium‐dihydride, which is considered the active species in the hydrogenation reactions.

This review will be centered around the work that has been reported on the development of metal–organic frameworks (MOFs) serving as catalysts for the conversion of carbon dioxide into short-chain hydrocarbons and the generation of clean energies starting from biomass. MOFs have mainly been used as support for catalysts or to prepare catalysts derived from MOFs (as sacrifice template), obtaining interesting results in the hydrogenation or oxidation of biomass. They have presented a good performance in the hydrogenation of CO2 into light hydrocarbon fuels. The common patterns to be considered in the performance of the catalysts are the acidity of MOFs, metal nodes, surface area and the dispersion of the active sites, and these parameters will be discussed in this review.

The catalytic activities of palladium complexes containing phosphorus-nitrogen ligands is reported. The catalysts studied showed high activities in the aminocarbonylation of aryl iodides. The palladium complexes reported activities between 100% and 58% in the aminocarbonylation reaction. The reactions are very selective for the double carbonylative amination of aryl halides. The major product is N,N-diethyl-α-oxo benzeneacetamide (96/4). The reaction was made under mild conditions of temperature and carbon monoxide pressure.

Aminocarbonylation of aryl halides, homogeneously catalysed by palladium, is an efficient method that can be employed for obtaining amides for pharmaceutical and synthetic applications. In this work, palladium (II) complexes containing P^N ligands were studied as catalysts in the aminocarbonylation of iodobenzene in the presence of diethylamine. Two types of systems were used: a palladium (II) complex formed in situ; and one prepared prior to the catalytic reaction. In general, the palladium complexes studied achieved high conversions in an average reaction time of less than 2 hr, which is less than that for the standard system (Pd (II)/PPh3) used. The pre‐synthesized complexes were faster than their in situ counterparts, as the latter require an induction time to form the Pd/P^N species. The structure and electronic properties of the ligand P^N can influence both the activity and the selectivity of the reaction, stabilizing the acyl‐palladium intermediates formed in a better manner.