Electronic coupling through intramolecular π-π interactions in biscobaltocenes: a structural, spectroscopic, and magnetic study

The paramagnetic dinuclear complexes 1,8-bis(cobaltocenyl)naphthalene (2) and 1,8-bis[(pentamethyl-η(5)-cyclopentadienyl)(η(5)-cyclopentadiendiyl)cobalt(II)]naphthalene (4) were synthesized. The molecular structures were characterized by X-ray structure analysis and consisted of two cobaltocenes linked through a distorted naphthalene clamp. Electronic interactions between the two cobalt atoms were observed by cyclic voltammetric studies. Superconducting quantum interference device (SQUID) measurements of the pure compounds and diluted in their diamagnetic iron derivatives, as well as variable-temperature NMR spectroscopy experiments in solution are presented. Magnetic measurements revealed an antiferromagnetic coupling of the electrons in complexes 2 and 4. From NMR spectroscopy experiments, Curie behavior in the temperature range from -60 to +60 °C can be deduced. The electronic structure and magnetic behavior is supported by results of broken-symmetry DFT and multireference calculations along with UV/Vis spectroscopic data, which revealed an intramolecular through space π-π interaction between the cobaltocene units.     

Unravelling the reaction path of rhodium-MonoPhos-catalysed olefin hydrogenation

The mechanism of the asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate (mac) catalysed by [Rh(MonoPhos)(2)(nbd)]SbF(6) (MonoPhos: 3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine) was elucidated by using (1)H, (31)P and (103)Rh NMR spectroscopy and ESI-MS. The use of nbd allows one to obtain in pure form the rhodium complex that contains two units of the ligand. In contrast to the analogous complexes that contain cis,cis-1,5-cyclooctadiene (cod), this complex shows well-resolved NMR spectroscopic signals. Hydrogenation of these catalyst precursors at 1 bar total pressure gave rise to the formation of a bimetallic complex of general formula [Rh(MonoPhos)(2)](2)(SbF(6))(2); no solvate complexes were detected. In the dimeric complex both rhodium atoms are ligated to two MonoPhos ligands but, in addition, each rhodium atom also binds to one of the binaphthyl rings of a ligand that is bound to the other rhodium metal. Upon addition of mac, a mixture of diastereomeric complexes [Rh(MonoPhos)(2)(mac)]SbF(6) is formed in which the substrate is bound in a chelate fashion to the metal. Upon hydrogenation, these adducts are converted into a new complex [Rh(MonoPhos)(2){mac(H)(2)}]SbF(6) in which the methyl phenylalaninate mac(H)(2) is bound through its aromatic ring to rhodium. Addition of mac to this complex leads to displacement of the product by the substrate. No hydride intermediates could be detected and no evidence was found for the involvement at any stage of the process of complexes with only one coordinated MonoPhos. The collected data suggest that the asymmetric hydrogenation follows a Halpern-like mechanism in which the less abundant substrate-catalyst adduct is preferentially hydrogenated to phenylalanine methyl ester.     

Sensitivity improvement in laser ablation inductively coupled plasma mass spectrometry achieved using a methane/argon and methanol/water/argon mixed gas plasma

The influence of the addition of carbon using methane or methanol/water to an inductively coupled plasma (ICP) via the carrier gas flow on the sensitivity in laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was studied. During the ablation of SRM NIST 610 with simultaneous addition of CH(4) (0.6-1.4 ml min(-1)), a sensitivity enhancement of more than one order of magnitude for selected analytes (e.g. (75)As(+)) was observed. In addition to the sensitivity enhancement for As, Te, I and Se, also all other measured elements showed a significantly enhanced sensitivity (minimum by a factor of 2). Potential mechanisms for the observed intensity enhancement include charge transfer reactions, a change in the ICP shape and a temperature increase in the plasma. Furthermore, the aspiration of a methanol-water mixture into a cooled spray chamber and the simultaneous addition to the laser ablated aerosol was investigated. This type of mixing leads to a sensitivity enhancement up to a factor of 20. To prevent clogging of the sampler cone and skimmer cone by carbon deposition, a fast cleaning procedure for the interface is tested during running ICP, which allows the application of such a set-up for specific applications.     

Anion binding by bambus[6]uril probed in the gas phase and in solution

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the binding of small anions to the macrocycle of bambus[6]uril. For the halide ions, the experimental patterns suggest F(-) < Cl(-) < Br(-) < I(-), which is consistent with the order of anion binding found in the condensed phase. Parallel equilibrium studies in the condensed phase establish the association constants of halide anions and bambus[6]uril in mixed solvents. A detailed analysis of the mass spectrometric data is used to shed light on the correlations between the binding constants in the condensed phase and the ion abundances observed using ESI-MS. From the analysis it becomes apparent that ESI-MS can indeed represent the situation in solution to some extent, but the sampling in the gas-phase experiment is not 1:1 compared to that in solution.     

Trinuclear rhodium hydride complexes

Three novel trinuclear rhodium hydride complexes of the type {[Rh(PP*)H](3)(μ(2)-H)(3)(μ(3)-H)}[BF(4)](2) containing diphosphines Tangphos, t-Bu-BisP* and Me-DuPHOS have been synthesised. The new compounds are very stable. Their structures have been characterized by X-ray analysis in the solid state and by NMR-spectroscopic investigations in solution.     

Systematic studies on the determination of Hg-labelled proteins using laser ablation-ICPMS and isotope dilution analysis

A method was developed for the precise and accurate determination of ovalbumin labelled with p-hydroxy-mercuribenzoic acid (pHMB) using polyacrylamide gel electrophoresis with ns-laser ablation–inductively coupled plasma mass spectrometry. Following systematic optimisation of the ablation process in terms of detection sensitivity, two different quantification strategies were applied: external calibration using standards of the derivatized protein after ¹³C⁺ normalization and, as a proof of concept, label-specific isotope dilution analysis (IDA) using pHMB enriched in the isotope ¹⁹⁹Hg. Due to the inhomogeneous distribution of the protein within the gel bands, it could be demonstrated that the IDA approach was superior in terms of precision and accuracy. Furthermore, it permits a reliable quantification, if more complex separation protocols are applied, as typically occurring analyte loss and degradation can be compensated for as soon as complete mixture of spike and sample is achieved. The estimated limit of detection was 160 fmol in the case of ovalbumin. In contrast to earlier studies using metals naturally present in proteins, no loss of mercury was observed during separation under denaturing conditions and other sample preparation steps. Using label-specific IDA, the measured isotope ratios in the gel corresponded to recoveries between 95% and 103%.     

A new series of 2-alkoxy(aralkoxy)-[1,2,4]triazolo[1,5-a]quinazolin-5-ones as adenosine receptor antagonists

This research was carried out to study the pharmacological activity of a newly synthesized series of 2-alkoxy-[1,2,4]triazolo[1,5-a]quinazolin-5-ones as adenosine receptor antagonists. These compounds have been tested in radioligand binding assays on cloned Chinese hamster ovary (CHO) cells transfected with A(1), A(2A), A(2B) and A(3) receptors. In particular, among the triazoloquinazolines (1-11), the dialkoxy derivative (7b) was found to have the highest affinity at A(1) subtype receptor, and its radioligand binding activity together with 1,3-dipropyl-8-cyclopentylxanthine (DPCPX) was studied. Finally, the structure-activity relationship (SAR) studies on the titled compounds provide some new insights about steric hindrance and lipophilic requirements for anchoring to the adenosine receptors recognition site.     

On the mechanism of the copper-mediated C-S bond formation in the intramolecular disproportionation of imine disulfides

The mechanism of the copper-mediated disproportionation of aromatic imine disulfides to benzothiazoles in the gas phase is investigated by experimental and theoretical methods. Application of infrared multiphoton dissociation and hydrogen/deuterium exchange experiments combined with density functional theory (DFT) calculations of the relevant molecular structures and the associated infrared spectra allows the identification of the observed ionic intermediates. The theoretical investigation of the possible reaction pathways supported by collision-induced dissociation experiments provides a consistent mechanistic picture of the reaction catalyzed by a single copper(I) ion. Activation of the substrate proceeds via homolytic sulfur-sulfur bond cleavage, yielding metal complexes in the formal +3 oxidation state; carbon-sulfur coupling and hydrogen-atom transfer complete the transformation to the products. Exploratory studies demonstrate that in the gas phase, the disproportionation of the imine disulfide can also be mediated by other metal ions via different either homo- or heterolytic mechanisms without involving high-valent intermediates.     

Synthesis, complexation behavior and application of a new diphosphite ligand in rhodium-catalyzed hydroformylation

Oxidative coupling of 3-(3-tert-butyl-4-hydroxyphenyl)propionic acid methyl ester (2) gave dimethyl 3,3′-(5,5′-di-tert-butyl-6,6′-dihydroxybiphenyl-3,3′-diyl)-dipropionate (1c), which upon phosphorylation/transesterification with a phosphochloridite derived from (R)-binaphthol, formed the new unsymmetrical binaphthol-bridged diphosphite 4. A rhodium catalyst based on 4 as ligand gave predominantly iso-selectivity in the hydroformylation of selected styrenes but opposite regioselectivity with 2,6-disubstituted derivatives. New chelate metal complexes (acac)RhL, PdCl₂L and PtCl₂L have been synthesized by reacting 4 with (acac)Rh(CO)₂, PdCl₂(MeCN)₂ and PtCl₂(COD), respectively. The structure of obtained compounds is determined based on ¹H, ¹³C, ³¹P and ¹⁹⁵Pt NMR spectroscopy and mass spectrometry data.     

Novel concept for the mass spectrometric determination of absolute isotopic abundances with improved measurement uncertainty: Part 2 – Development of an experimental procedure for the determination of the molar mass of silicon using MC-ICP-MS

The isotopic abundances and thus molar mass M(Si) of a silicon crystal material with natural isotopic abundances have been measured for the first time using multicollector-ICP-mass spectrometry (MC-ICP-MS) in combination with a novel concept of a modified isotope dilution mass spectrometry (IDMS)-method. This experimental work is the further development of part 1 of this series of papers. While part 1 describes the theoretical background and the mathematical derivation of the novel concept in detail, the measurements presented here serve to validate the novel concept and give experimental proof of its capability. Moreover, the also new method for the analytical calculation of calibration factors needed in the determination of absolute isotope amount ratios has been tested successfully. Silicon isotopic abundances have been measured directly from an aqueous alkaline matrix following a new sample preparation protocol developed within the framework of this study. A molar mass of M(Si) = 28.08548(13) g/mol with an associated relative uncertainty of u_rel = 4.6 × 10^?6 (k = 1) has been measured. This is in excellent agreement with the current IUPAC value for the molar mass of natural silicon M(Si_nat) = 28.08550(15) g/mol with u_rel = 5.3 × 10^?6 (k = 1). An uncertainty budget according to the Guide to the Expression of Uncertainty in Measurement (GUM) was calculated to assess the presented results and to validate the novel concept with the help of experimental data. The development of a new experimental procedure is presented in detail and the contributions to the uncertainty are discussed in comparison to part 1 of this work.