Versatile palladium-catalyzed double carbonylation of aryl bromides.

A versatile palladium-catalyzed double carbonylation of aryl bromides has been developed. Using Pd(OAc)2/BuPAd2 as the catalyst system and DBU as the base, under relatively low CO pressure, various α-ketoamides were produced in good yields. In order to get insight into the reaction pathway, real time NMR studies were performed as well and a correlated reaction mechanism is been given.

CO2 as a hydrogen vector - transition metal diamine catalysts for selective HCOOH dehydrogenation.

The homogeneous catalytic dehydrogenation of formic acid in aqueous solution provides an efficient in situ method for hydrogen production, under mild conditions, and at an adjustable rate. We synthesized a series of catalysts with the chemical formula [(Cp*)M(N-N')Cl] (M = Ir, Rh; Cp* = pentamethylcyclopentadienyl; N-N = bidentate chelating nitrogen donor ligands), which have been proven to be active in selective formic acid decomposition in aqueous media. The scope of the study was to examine the relationship between stability and activity of catalysts for formic acid dehydrogenation versus electronic and steric properties of selected ligands, following a bottom-up approach by increasing the complexity of the N,N'-ligands progressively. The highest turnover frequency, TOF = 3300 h-1 was observed with a Cp*Ir(iii) complex bearing 1,2-diaminocyclohexane as the N,N'-donor ligand. From the variable temperature studies, the activation energy of formic acid dehydrogenation has been determined, Ea = 77.94 ± 3.2 kJ mol-1. It was observed that the different steric and electronic properties of the bidentate nitrogen donor ligands alter the catalytic activity and stability of the Ir and Rh compounds profoundly.

Calorimetric and spectroscopic studies on solvation energetics for H2 storage in the CO2/HCOOH system.

Solvents playing a crucial role in many chemical reactions and additives can be used to shift the reaction equilibrium. Herein we study the enthalpy of mixing for selected solvents (aqueous, organic) and basic additives (amines, aqueous KOH) when mixed with formic acid with the aim to optimize hydrogen storage/delivery in the CO2/HCOOH system. Formic acid, resulting from carbon dioxide hydrogenation, reaches highest yields when effectively "removed" from the reaction equilibrium. In terms of energy efficiency, any heat released during CO2 hydrogenation has to be reused in the reverse reaction, during the production of hydrogen. In any scenario, the usage of basic chemicals, non-innocent solvents, causes higher energy release in CO2 hydrogenation, which has to be reused in the hydrogen delivery process. Therefore, the enthalpy of mixing is a valuable parameter for designing hydrogen storage devices since it allows the estimation of energy balance for the CO2 hydrogenation/H2 liberation cycle. The highest formic acid concentrations in direct catalytic CO2 hydrogenation under acidic conditions were reached in DMSO. DMSO exhibits considerably stronger interactions with formic acid compared to water as was observed in calorimetric measurements. This difference can be ascribed, at least partly, to stronger hydrogen bonding of FA to DMSO than to water in the corresponding solutions, examined by a combination of IR spectroscopic and quantum chemical studies. Furthermore, the investigation of DMSO/FA- and water/FA systems by (1)H- and (13)C-NMR spectroscopy revealed that only 1 : 1 aggregates are formed in the DMSO solutions of FA in a broad concentration range, while the stoichiometry and the number of the FA-water aggregates essentially depend on the concentration of aqueous solutions.

Hydrogen Storage in the Carbon Dioxide - Formic Acid Cycle.

This year Mankind will release about 39 Gt carbon dioxide into the earth's atmosphere, where it acts as a greenhouse gas. The chemical transformation of carbon dioxide into useful products becomes increasingly important, as the CO(2) concentration in the atmosphere has reached 400 ppm. One approach to contribute to the decrease of this hazardous emission is to recycle CO(2), for example reducing it to formic acid. The hydrogenation of CO(2) can be achieved with a series of catalysts under basic and acidic conditions, in wide variety of solvents. To realize a hydrogen-based charge-discharge device ('hydrogen battery'), one also needs efficient catalysts for the reverse reaction, the dehydrogenation of formic acid. Despite of the fact that the overwhelming majority of these reactions are carried out using precious metals-based catalysts (mainly Ru), we review here developments for catalytic hydrogen evolution from formic acid with iron-based complexes.

Synthesis, radiosynthesis and first in vitro evaluation of novel PET-tracers for the dopamine transporter: [(11)C]IPCIT and [(18)F]FE@IPCIT.

INTRODUCTION: Present data indicate that merging beneficial structural elements from previously published DAT-ligands highest DAT affinity, selectivity and a suitable metabolic profile should be achieved. This combination led to the development of IPCIT and FE@IPCIT. METHODS: Precursor synthesis was done starting from cocaine in a six step reaction. O-[(11)C]-methylation was established using [(11)C]methyl iodide, optimized and subsequently automated. Small scale (18)F-fluroroethylation as well as optimization of reaction parameters and automation were performed. Affinity and selectivity of the candidate substances were tested in standard binding experiments on human membranes. Metabolic stability and blood-brain-barrier (BBB) penetration were determined. RESULTS: Precursor compound, IPCITacid, and reference compounds, IPCIT and FE@IPCIT, were obtained in 4.9%, 12.7% and 4.1% yield, respectively. Automated radiosynthesis of [(11)C]IPCIT yielded 1.9 ± 0.7 GBq (12.5 ± 4%, corrected for decay). Optimum parameters for (18)F-fluoroethylation were 110 °C for 15 min under TBAH catalysis, yielding 67 ± 16 % radiochemical incorporation. Affinity was determined as 1.7 ± 0.6 nM for IPCIT, 1.3 ± 0.2 nM for FE@IPCIT and 37 ± 13 nM for the precursor molecule, IPCIT-acid. Results from in vitro and in silico evaluations revealed high stability but also high lipophilicity. CONCLUSION: Present data indicate high affinity and stability of both IPCIT and FE@IPCIT. Radiolabelling, optimization of reaction parameters and automation succeeded. On the other hand, data concerning BBB-penetration are not promising.