Ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the study of Pt electro-dissolution.

There is an ongoing debate regarding the mechanism of Pt electrochemical dissolution. However, only off-line methods have so far been used, where separation of Pt species is performed separately from their detection. In this study, ion exchange chromatography coupled to inductively coupled plasma mass spectrometry was used for the first time to separate and detect Pt species generated by the electro-dissolution of a Pt electrode in 0.5M aqueous H2SO4 solution. Because these species are either neutral or cationic, they were converted to chloro-complexes using 0.1M KCl to enable their separation by anion exchange chromatography. Chloro-aqua complexes were observed in addition to the two predominant species, namely PtCl4(2-) and PtCl6(2-). A good linear relationship was observed between the sum of peak areas for all complexes of a given Pt oxidation state and the Pt concentration, with a detection limit of 0.1 µg L(-1) being reached for Pt(II) and Pt(IV). Application of this speciation analysis method to real samples generated by potential cycling using cyclic voltammetry (CV) revealed that, in general, at least 80% of Pt was present as Pt(II), irrespectively of the cyclic potential range or of temperature (up to 60°C). Still, quantitative spike recovery was achieved after adding known amounts of Pt(II) or Pt(IV) to a sample prepared by CV, which demonstrated that no significant species inter-conversion took place.

Amine exchange in formamidines: an experimental and theoretical study.

N-H-containing formamidines combine a reasonably strong association to carboxylic acids to form complexes of well-defined geometries with a simultaneous proton-induced electrophilicity enhancement that allows for the exchange of their amine portion. The N=C(H)-NH fragment, therefore, undergoes "imine-like" exchange with N-containing nucleophiles. Because of the prototropic equilibrium, the N=C(H)-NH fragment may behave as a "bisimine" centred on the same carbon, in which both N-containing fragments can be exchanged. Considering the proton-induced sensitisation of both C-N units and the well-defined formamidine-carboxylic acid complex geometry, it should be possible to use carboxylic acids as templates for the synthesis of defined architectures by dynamic amine exchange within formamidines. This study highlights three exchange regimes based on the nature of the incoming amine (aliphatic amines, aromatic amines and alkoxyamines), as well as exchange rules based on the amine leaving groups. Following this analysis, a proof of concept for carboxylic acid templated macrocycle formation through dynamic exchange is provided.

Stereochemical and conformational exchanges in N,N'-di(2-pyridyl)formamidines: An X-ray and (1)H NMR study.

The solid state structure of N,N'-di(2-pyridyl)formamidine displays a four-hydrogen-bonded dimer. In solution, two isomers are observed, one of which is selected and amplified either by crystallization or by adding protons. Solution state analysis of N,N'-di(2-pyridyl)formamidines reveals the presence of the uncommon Z formamidine isomer, which equilibrates with the E-isomer with an activation energy of 90 kJ mol(-1) in CDCl(3).

Design and synthesis of urea-linked aromatic oligomers--a route towards convoluted foldamers.

Herein we report the design and synthesis of crescent-shaped and helical urea-based foldamers, the curvature of which is controlled by varying the constituent building blocks and their connectivity. These oligomers are comprised of two, three or five alternating aromatic heterocycles (pyridazine, pyrimidine or pyrazine) and methyl-substituted aromatic carbocycles (tolyl, o-xylyl or m-xylyl) connected together through urea linkages. A crescent-shaped conformational preference is encoded within these pi-conjugated urea-linked oligomers based on intramolecular hydrogen bonding and steric interactions; the degree of curvature is tuned by the urea connectivity to the heterocycles and the aryl groups. NMR characterization of these foldamers confirms the intramolecular hydrogen-bonded conformation expected (Z,E configuration of the urea bond) in both the pyridazyl and pyrimidyl foldamers in solution. An X-ray crystal structure of the N(3),N(6)-diisobutylpyridazine-4,6-diamine-o-tolyl urea-linked foldamer (4) confirms the presence of N-H...N hydrogen bonds between the heterocyclic nitrogen atom and the free hydrogen of the urea linkage. Additionally, the tolyl methyl group interacts unfavourably with the urea carbonyl oxygen, thus destabilising the alternate planar conformation.

Hydrogen bond directed synthesis of pyridazine and naphthyridine containing macrocycles.

This work describes a high-yielding, one-step synthesis of pyrizadine and naphthyridine containing macrocycles directed by intramolecular H-bonding.