Kinetics of the reversible reaction between arsenious acid and aqueous iodine

The kinetics of the reversible reaction have been studied spectrophotometrically in acid solution under conditions in which both the forward and reverse reactions go to virtual completionand in which the reaction comes to a practical equlibrium. The rates of theforward (R_f) and reverse (R_r) reactions are given by where f, g, h, u, and v have the values (4 ± 1) × 10^?5 mole/1.·s, (4.2 ± 0.2) × 10^?5 mole²/1.²·s, (5.0 · 0.3) × 10^?7 mole³/1.³·s, (1.1 ± 0.1) × 10^?3 1.²/mole²·s, and (3.7 ± 0.2) × 10^?3 1.³/mole³·s at 298.2°K and at an ionic strength of 2.00M maintained by adding sodium chloride. The stoichiometric equilibrium constant under similar conditions is 0.022 ± 0.003. Differentvalues of these parameters were obtained when sodium perchlorate and sodiumnitrate were used to control ionic strength. The results are compared with those from previous reports and a mechanism is proposed based upon an initial rapid equilibrium followed by a rate-determining attack of water upon H₃AsO₃I⁺, H₂AsO₃I, and HAsO₃I^?.     

Kinetics and mechanism of oxidation of arsenious acid by tetrachloroaurate(III) in hydrochloric acid medium

Kinetics of the oxidation of arsenious acid by tetrahcloroaurate(III) have been studied spectrophotometrically in hydrochloric acid medium. Initial complex formation between As(III) and Au(III) followed by the decomposition of the intermediate complex to give products of the reaction is suggested. The empirical rate law is

k and K are found to be 13.9 × 10^?4 s^?1 and 24.2 M^?1 respectively at 30°C and μ = 1.0 M. ΔH³ and ΔS³ for k are found to be 49.2 kJ mol^?1 and - 137.2 JK^?1 mol^?1 whereas ΔH and ΔS associated with K are - 6.75 kJ mol^?1 and 4.14 JK^?1 respectively.     

Kojic acid derivatives as histamine H(3) receptor ligands

The histamine H(3) receptor (H(3)R) is a promising target in the development of new compounds for the treatment of mainly centrally occurring diseases. However, emerging novel therapeutic concepts have been introduced and some indications in the H(3)R field, e.g. migraine, pain or allergic rhinitis, might take advantage of peripherally acting ligands. In this work, kojic acid-derived structural elements were inserted into a well established H(3)R antagonist/inverse agonist scaffold to investigate the bioisosteric potential of γ-pyranones with respect to the different moieties of the H(3)R pharmacophore. The most affine compounds showed receptor binding in the low nanomolar concentration range. Evaluation and comparison of kojic acid-containing ligands and their corresponding phenyl analogues (3-7) revealed that the newly integrated scaffold greatly influences chemical properties (S Log P, topological polar surface area (tPSA)) and hence, potentially modifies the pharmacokinetic profile of the different derivatives. Benzyl-1-(4-(3-(piperidin-1-yl)propoxy)phenyl)methanamine ligands 3 and 4 belong to the centrally acting diamine-based class of H(3)R antagonist/inverse agonist, whereas kojic acid analogues 6 and 7 might act peripherally. The latter compounds state promising lead structures in the development of H(3)R ligands with a modified profile of action.     

Fluoroarylphosphines as ligands

This short review concentrates on important aspects of fluoroarylphosphines, in particular their synthesis, ligand properties and chemical and catalytic properties of their complexes. Although the electronic, steric and chemical properties of fluoroarylphosphines have been known for 30 years, their use as ligands for homogeneous catalysis and in the synthesis of elaborate multidentate ligands has occurred more recently. The number of recent reports suggests that their importance is growing.     

High-precision gravimetric coulometry using the silver-perchloric acid coulometer: Titration of arsenious oxide with electrogenerated iodine

High-precision gravimetric coulometry with a silver-perchloric acid coulometer is evaluated as an alternative to the conventional titrimetric method. The loss of weight (caused by electrolytic dissolution) of a highly pure silver anode in series with the cathode of a conventional constant-current titration system is measured and related to the number of equivalents of substance titrated. The precision of the method is determined by titrations of the Standard Reference Material 83C arsenious oxide (99.99% pure) with electrogenerated iodine, using biamperometric end-point detection. Depending on the size of the sample, an ultimate precision of 25 ppm is obtained. The assay for 0.5-g samples of the SRM material is 99.993(9) +/- 0.002(5)% purity.     

Derivatives of phosphorous acid as a new class of ligands for Pd-catalyzed allylation

Amido- and aminophosphites and hydrospirophosphoranes can be used as ligands in the Pd-catalyzed allylation of ethyl malonate with ethyl (3-phenylprop-2-enyl) carbonate. Bidentate ligands (RO)₂P--O(CH₂)_n--NR"₂ (n = 2 and 3) were found to be the most effective ligands.     

Carbohydrate-based DNA ligands: sugar-oligoamides as a tool to study carbohydrate-nucleic acid interactions

Sugar-oligoamides have been designed and synthesized as structurally simple carbohydrate-based ligands to study carbohydrate-DNA interactions. The general design of the ligands 1-3 has been done as to favor the bound conformation of Distamycin-type gamma-linked covalent dimers which is a hairpin conformation. Indeed, NMR analysis of the sugar-oligoamides in the free state has indicated the presence of a percentage of a hairpin conformation in aqueous solution. The DNA binding activity of compounds 1-3 was confirmed by calf thymus DNA (ct-DNA) NMR titration. Interestingly, the binding of the different sugar-oligoamides seems to be modulated by the sugar configuration. Semiquantitative structural information about the DNA ligand complexes has been derived from NMR data. A competition experiment with Netropsin suggested that the sugar-oligoamide 3 bind to DNA in the minor groove. The NMR titrations of 1-3 with poly(dA-dT) and poly(dG-dC) suggested preferential binding to the ATAT sequence. TR-NOE NMR experiments for the sugar-oligoamide 3-ct-DNA complex both in D(2)O and H(2)O have confirmed the complex formation and given information on the conformation of the ligand in the bound state. The data confirmed that the sugar-oligoamide ligand is a hairpin in the bound state. Even more relevant to our goal, structural information on the conformation around the N-glycosidic linkage has been accessed. Thus, the sugar asymmetric centers pointing to the NH-amide and N-methyl rims of the molecule have been characterized.     

Mass spectra of organoarsenic compounds—I: Electron-impact-induced fragmentations of esters of arsenious and thioarsenious acid

The mass spectra of a series of esters of arsenious and thioarsenious acid have been studied, together with that of diethyl methylarsonite. The main fragmentation pathways have been determined with the use of high resolution mass measurements and application of the metastable defocusing technique. The major fragment ions all contain arsenic and may be ascribed structures implying divalent/trivalent arsenic. Ions implying tetravalent/pentavalent arsenic as well as double hydrogen rearrangement processes are hardly recognisable; this is in contrast to the findings reported for the corresponding phosphorous compounds, with which a comparison is made. The present results are in accordance with the view that arsenic is less capable than phosphorous of achieving multiple bonding to other atoms by means of its empty d orbitals.     

Dicarbonylcyclopentadienyltellurophenyliron complexes as ligands

The reaction of CpFe(CO)₂TePh (I) with ferricinium hexafluorophosphate as an oxidant affords ionic complex {[CpFe(CO)₂]₂(μ-TePh)}⁺PF ₆ ^? (II) with the simultaneous formation of diphenylditellurium. The decarbonylation of compound II by Me₃NO followed by the addition of complex I affords trinuclear complex {[CpFe(CO)₂(μ-TePh)]₂Fe(CO)Cp}PF₆ (III). The corresponding tetrafluoroborate (IV) is synthesized similarly. The heating of compound I with PPh₃ gives CpFe(CO)(PPh₃)TePh (V) that reacts with ionic complex [CpMn(CO)₂(NO)]PF₆ (VI) to form binuclear heterometallic ionic complex [CpFe(CO)(PPh₃)(μ-TePh)Mn(CO)(NO)Cp]PF₆ (VII). A similar reaction of Cp′Fe(CO)₂TePh (Cp′ is methylcyclopentadienyl) with compound VI affords heterometallic [Cp′Fe(CO)₂(μ-TePh)Mn(CO)(NO)Cp]PF₆ (VIII). The structures of compounds II, IV, VII, and VIII are determined by X-ray diffraction analysis (CIF files CCDC 963285, 963286, 963288, and 963289, respectively).     

Complexation of metal ions with TRAP (1,4,7-triazacyclononane phosphinic acid) ligands and 1,4,7-triazacyclononane-1,4,7-triacetic acid: phosphinate-containing ligands as unique chelators for trivalent gallium

Three phosphinic acid 1,4,7-triazacyclononane (TACN) derivatives bearing methylphosphinic (TRAP-H), methyl(phenyl)phosphinic (TRAP-Ph), or methyl(hydroxymethyl)phosphinic acid (TRAP-OH) pendant arms were investigated as members of a new family of efficient Ga(3+) chelators, TRAP ligands (triazacyclononane phosphinic acids). Stepwise protonation constants of ligands and stability constants of their complexes with Ga(3+), selected divalent metal, and Ln(3+) ions were determined by potentiometry. For comparison, equilibrium data for the metal ion-NOTA (1,4,7-triazacyclononane-1,4,7-triacetic acid) systems were redetermined. These ligands exhibit high thermodynamic selectivity for Ga(3+) over the other metal ions (log K(GaL) - log K(ML) = 7-9) and a selective complexation of smaller Mg(2+) over Ca(2+). Stabilities of the Ga(3+) complexes are dependent on the basicity of the donor atoms: [Ga(NOTA)] (log K(GaL) = 29.6) > [Ga(TRAP-OH)] (log K(GaL) = 23.3) > [Ga(TRAP-H)] (log K(GaL) = 21.9). The [Ga(TRAP-OH)] complex exhibits unusual reversible rearrangement of the "in-cage" N(3)O(3) complex to the "out-of-cage" O(6) complex. The in-cage complex is present in acidic solutions, and at neutral pH, Ga(3+) ion binds hydroxide anion, induces deprotonation and coordination of the P-hydroxymethyl group(s), and moves out of the macrocyclic cavity; the hypothesis is supported by a combination of results from potentiometry, multinuclear nuclear magnetic resonance spectrometry, and density functional theory calculations. Isomerism of the phosphinate Ga(3+) complexes caused by a combination of the chelate ring conformation, the helicity of coordinated pendant arms, and the chirality of the coordinated phosphinate groups was observed. All Ga(3+) complexes are kinetically inert in both acidic and alkaline solutions. Complex formation studies in acidic solutions indicate that Ga(3+) complexes of the phosphinate ligands are formed quickly (minutes) and quantitatively even at pH <2. Compared to common Ga(3+) chelators (e.g., 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) derivatives), these novel ligands show fast complexation of Ga(3+) over a broad pH range. The discussed TRAP ligands are suitable alternatives for the development of (68)Ga radiopharmaceuticals.     

NHC ligands versus cyclopentadienyls and phosphines as spectator ligands in organometallic catalysis

N-heterocyclic carbenes are compared with cyclopentadienyls and phosphines in terms of bonding and reactivity. Synthetic difficulties that currently prevent the general incorporation of NHCs into chelate, pincer and tripod ligand architectures are related to the inability of the NHC to reversibly decoordinate to correct binding ‘errors’ in the initial kinetic products of NHC complex formation. The strengths and weaknesses of current synthetic approaches, such as Lin’s Ag₂O transmetallation route, are discussed. Linker dependent reactivity patterns are related to azole ring orientation effects and some aspects of cyclometalation are considered.