Geochemical evidence for the link between sulfate reduction, sulfide oxidation and phosphate accumulation in a Late Cretaceous upwelling system.

Background: On Late Cretaceous Tethyan upwelling sediments from the Mishash/Ghareb Formation (Negev, Israel), bulk geochemical and biomarker analyses were performed to explain the high proportion of phosphates in the lower part and of organic matter (OM) preserved in upper parts of the studied section. The profile is composed of three facies types; the underlying Phosphate Member (PM), the Oil Shale Member (OSM) and the overlying Marl Member (MM).

Results: Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.

Gutmann donor and acceptor numbers for ionic liquids.

We present for the first time Gutmann donor and acceptor numbers for a series of 36 different ionic liquids that include 26 distinct anions. The donor numbers were obtained by (23)Na NMR spectroscopy and show a strong dependence on the anionic component of the ionic liquid. The donor numbers measured vary from -12.

Coordination of 1,10-phenanthroline and 2,2'-bipyridine to Li+ in different ionic liquids. How innocent are ionic liquids?

On the basis of (7)Li NMR measurements, we have made detailed studies on the influence of the ionic liquids [emim][NTf(2)], [emim][ClO(4)], and [emim][EtSO(4)] on the complexation of Li(+) by the bidentate N-donor ligands 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen). For each of the employed ionic liquids the NMR data implicate the formation of [Li(bipy)(2)](+) and [Li(phen)(2)](+), respectively. X-ray diffraction studies were performed to determine the coordination pattern in the solid state.

Understanding chemical reaction mechanisms in ionic liquids: successes and challenges.

The focus of this article is an examination of chemical reaction mechanisms in ionic liquids. These mechanisms are compared with those pertaining to the same reactions carried out in conventional solvents. In cases where the mechanisms differ, attempts to provide an explanation in terms of the chemical and physicochemical properties of the reactants and of the components of the ionic liquids are described.

Is bis(trifluoromethylsulfonyl)amide an innocent anion? X-ray structure data and DFT calculations.

The coordinative behaviour of the bis(trifluoromethylsulfonyl)amide (NTf2-) anion was studied in terms of its interaction with the labile [Pd(terpyridine)Cl]Cl complex. Among various attempts to coordinate NTf2- to the Pd(II) centre, the complexes [Pd(terpyridine)NO3]NTf2 and [Pd(terpyridine)H2O](NTf2)2 were isolated and characterized. The crystallographic data for these complexes are presented and the possible coordination of the NTf2- anion to the metal centre is discussed in reference to DFT predictions.

Fast substitution reactions of Pt(II) in different ionic liquids. reactivity control by anionic components.

The effect of several imidazolium-based ionic liquids on the rate and mechanism of the substitution reaction of [Pt(terpyridine)Cl](+) with thiocyanate was investigated as a function of thiocyanate concentration and temperature under pseudo-first-order conditions using stopped-flow and other kinetic techniques. The obtained rate constants and activation parameters showed good agreement with the ion-pair stabilization energies between the anions of the ionic liquids and the cationic Pt(II) complex derived from density-functional theory calculations (RB3LYP/LANL2DZp) and with parameters derived from the linear solvation energy relationship set by the Kamlet-Taft beta parameter, which is a measure of a solvent's hydrogen bonding acceptor ability. In general, the substitution reactions followed an associative mechanism as found for conventional solvents, but the observed rate constants showed a significant dependence on the nature of the anionic component of the ionic liquid used as solvent.

Mechanistic studies on fast ligand substitution reactions of Pt(II) in different ionic liquids: role of solvent polarity and ion-pair formation.

The effect of several imidazolium-based ionic liquids on the mechanism of a classical ligand substitution reaction of [Pt(terpyridine)Cl] (+) with thiourea was investigated. A detailed kinetic study as a function of the nucleophile concentration and temperature was undertaken under pseudo-first-order conditions using stopped-flow techniques. Polarity measurements were performed for the employed ionic liquids on the basis of solvatochromic effects, and they show similarities with conventional polar solvents.

Heterogeneous electron transfer at Au/SAM junctions in a room-temperature ionic liquid under pressure.

Proven electrochemical approaches were applied to study heterogeneous electron transfer (ET) between selected redox couples and gold electrodes modified with alkanethiol self-assembled monolayers (SAMs), using the room-temperature ionic liquid (RTIL) [bmim][NTf2] as reaction medium; ferrocene as freely diffusing redox probe in the RTIL was tested for ET through both thin (butanethiol) and thick (dodecanethiol) assemblages at pressures up to 150 MPa; well behaved kinetic patterns and reproducibility of data were demonstrated for ET within the unique Au/SAM/RTIL arrays.

High-pressure testing of heterogeneous charge transfer in a room-temperature ionic liquid: evidence for solvent dynamic control.

We report the first application of a high-pressure electrochemical strategy to study heterogeneous charge transfer (CT) in a room-temperature ionic liquid, [BMIM][BTA]. High-pressure kinetic studies on electron exchange for two redox couples of different charge type, viz. [Fe(bipy)3]3+/2+ and [Fe(cp)2]+/0, at bare Au electrodes within the range of 0.

Rapid ligand substitution reactions in ionic liquids studied by stopped-flow technique.

Detailed kinetic studies on ligand substitution reactions of [M(II)(terpy)Cl](+) complexes (M = Pt, Pd; terpy = 2,2':6',2''-terpyridine) with thiourea as entering nucleophile were for the first time performed in the imidazolium based ionic liquid [emim][NTf(2)] using stopped-flow techniques, opening the route to study fast reactions of transition metal complexes in ionic liquids.