Kinetics of dissociation of tris-1,10-phenanthroline-iron(II) complex cation in aqueous acetic acid solutions

The reaction under study is first order in the complex ion over the entire composition range of the mixed solvent. A minimum amount of mineral acid is needed for completion of the reaction (formation of colorless products), but the rate is practically acid-independent. The influence of solvent composition and some common ions on the reaction rate have been examined. A reaction mechanism consistent with the rate behavior is proposed where water is shown as an active participant in the dissociation process. A plausible explanation for the retardation effect of HSO₄ ⁻ as against the accelerating effect of Cl⁻ under water-scarce conditions is provided.     

The determination of thallium(III) with the 2,2'-bipyridyl-iron(II) chelate

A spectrophotometric determination of thallium (III), based on solvent extraction of an ion-association pair formed between the cationic 2,2'-bipyridyl-iron(II) chelate and the anionic thallium(III) bromide complex is described. The best extractant is 1,2-dichloroethane and extraction is possible over the pH range 2.5–6.7. The composition of the extracted species was confirmed, and conditions were established for the extraction over the concentration range 7.9·10^-6–3.5·10^-5M of thallium in aqueous solution.     

Kinetics of dissociation of tris-(2,2'-bipyridyl) iron(II) in water solubilized by Triton X-100 reverse micelles

The dissociation of tris-(2,2'-bipyridyl) iron(II) ([Fe(bipy)3]2+) has been studied in the Triton X-100/hexanol/cyclohexane reverse micellar medium. The reaction obeys simple first-order kinetics with no evidence of autoinhibition. The first-order rate constant (k1) has been determined at different values of W ([H2O]/[Triton X-100]). The rate (k1) decreases with increasing value of W. k1 also increases with increase in Triton X-100 concentration at constant values of W, showing that the reaction takes place at greater speed at the micellar interface. The kinetic results can be interpreted by the monomolecular pseudo-phase model. The effect of W on rate (k1) is more pronounced in the range of W from 1.55 to 4.2 but less pronounced at higher W. The reaction is further accelerated by Cl- and SCN- ions and the kinetic results provide evidence for the formation of ion pairs between the cation [Fe(bipy)3]2+ and each of these anions. The formation of such ion pairs has not been observed in aqueous medium but has been reported earlier in aqueous-alcohol mixtures. This result therefore provides evidence for the lower micropolarity of solubilized water compared to ordinary water.     

Protolytic dissociation of copper(II) and nickel(II) dipyrrolylmethenates in benzene solutions of acetic acid

Protolytic dissociation of copper(II) and nickel(II) dipyrrolylmethenates in benzene solutions of acetic acid has been studied. The results have completed the knowledge of kinetics of dipyrrolylmethene complexes dissociation in acidic medium. The effect of the nature of complex forming atom, ligand, and other factors on the complexes kinetic stability has been analyzed.     

Metallophilic interactions in iodido(2,2′:6′,2′′‐terpyridine)platinum(II) diiodidoaurate(I)

In the title compound, [PtI(C₁₅H₁₁N₃)][AuI₂], the [PtI(terpy)]⁺ cations (terpy is 2,2′:6′,2′′‐terpyridine) stack in pairs about inversion centers through Pt...Pt interactions of 3.5279 (5) Å. The [AuI₂]⁻ anions also exhibit pairwise stacking, with Au...I distances of 3.7713 (5) Å. The [PtI(terpy)]⁺ cations and [AuI₂]⁻ anions aggregate forming infinite arrays of stacked ...({[PtI(terpy)]⁺...[PtI(terpy)]⁺}...{[AuI₂]⁻...[AuI₂]⁻})... units.     

Kinetics and mechanism of formation and decay of 2,2′-azinobis-(3-ethylbenzothiazole-6-sulphonate) radical cation in aqueous solution by inorganic peroxides

The kinetics of oxidation of 2,2′-azinobis-(3-ethylbenzothiazole-6-sulphonate) (ABTS) by the inorganic peroxides, peroxomonosulphate, peroxodisulphate, peroxodiphosphate, and hydrogen peroxide were investigated in aqueous solution. The kinetics of formation of the radical cation, ABTS^.+, on one-electron abstraction by these peroxides and the further reaction of ABTS^.+ with higher concentrations of these peroxides at longer time scale were studied by following the growth and decay of the radical cation, ABTS^.+ at 417 nm. The rate of formation of ABTS^.+ was found to obey a total second-order, first-order each in [ABTS] and [peroxide], except for H₂O₂, which reacted through Michaelis-Menten kinetics. All the peroxides investigated were found to react with ABTS^.+; however peroxodisulphate alone oxidized ABTS^.+ to the dication (ABTS⁺⁺), the other peroxides reacted via ionic mechanism, probably forming sulphoxide and sulphone as products. The kinetics of decay of the radical cation, ABTS^.+, was also found to follow a total second-order, first-order each in [ABTS^.+] and [peroxide], except peroxodiphosphate the reaction of which obeyed Michaelis-Menten kinetics. The effect of pH and temperature were also investigated in all the systems and the kinetic and thermodynamic parameters were evaluated and discussed with suitable reaction mechanisms.     

Kinetics of reactions of the tris-(4-methyl-1,10-phenanthroline)iron(II) cation

Summary Kinetic parameters are reported for aquation of the tris-(4-methyl-1,10-phenanthroline) iron(II) [Fe(4-Mephen)₃]²⁺, cation and for its reactions with hydroxide, cyanide, and peroxodisulphate. Activation volumes have been determined for the two last-named reactions; they reflect the importance of solvation changes in transition state formation.     

Synthesis,Coordination, and Spectroscopic Properties of 2,2′‐Bipyridyldimesitylpalladium(II) and 6‐Mesityl‐2,2′‐bipyridyldimesitylpalladium(II)

The synthetic route to the dimesitylpalladium(II) complex [(bpy)PdMes₂] ( 1 ) (Mes = mesityl = 2,4,6‐trimethyl phenyl) does not only give the desired compound but also the 6‐mesityl‐2,2′bipyridyldimesitylpalladium [(6‐Mes‐bpy)PdMes₂] ( 2 ) complex and the free ligand 6,6′‐dimesityl‐2,2′‐bipyridine in reasonable yields. Single crystals of 2 were examined by X‐Ray diffraction. The compound reveals a sterically crowded molecular structure. An intramolecular π‐stacking interaction was found between the mesityl substituent on the bipyridine ligand and the adjacent mesityl ligand. The electrochemical behaviour of 1 and 2 together with a related compound was examined at various temperatures showing two reversible reduction reactions and reversible one‐electron oxidation steps at low temperatures. The latter are assigned to Pd^II/Pd^III couples.     

Photophysical Properties and Photochemical Behaviour of Ruthenium(II) complexes containing the 2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine ligands

The temperature dependence of the emission lifetime of the series of complexes Ru(bpy)_n(4,4′-dpb) (bpy = 2,2′bipyridine, 4,4′-dpb = 4,4′-diphenyl-2,2′-bipyridine) has been studied in propionitrile/butyronitrile (4:5 v/v) solutions in the range 90–293 K. The obtained photophysical parameters show that the energy separation between the metal-to-ligand charge tranfer (³MLCT) emitting level and the photoreactive metal-centered (³MC) level changes across the series (ΔE = 3960, 4100, 4300, and 4700 cm^?1 for Ru(bpy)), Ru(bpy)2(4,4′-dpb)²⁺, Ru(bpy)(4,4′-dpb), and Ru(4,4′-dpb), respectively, where ΔE is the energy separation between the minimum of the ³MLCT potential curve and ³MLCT – ³MC crossing point. Comparison between spectral and electrochemical data indicated that the changes in ΔE are due to stabilization of the MLCT levels in complexes containing 4,4′-dpb with respect to Ru(bpy)²⁺₃. The photochemical data for the same complexes (as I^? salts) have been obtained in CH₂Cl₂ in the presence of 0.01M Cl^? upon irradiation at 462 nm. The complexes containing 4,4′-dpb are more photostable than Ru(bpy). Comparison between the data for thermal population of the ³MC photoreactive state and those for photochemistry indicated that the overall photochemical process is governed by (i) a thermal redistribution between the emitting and photoreactive excited states, and (ii) mechanistic factors, likely related to the size of the detaching ligand.     

A novel copper(II) coordination polymer with 2,2′‐bipyridyl‐3,3′‐di­carboxylic acid

A novel copper(II) coordination polymer, poly­[[[aqua­copper(II)]‐μ₃‐2,2′‐bipyridyl‐3,3′‐di­carboxyl­ato‐κ⁴N,N′:O:O′] dihydrate], {[Cu(C₁₂H₆N₂O₄)(H₂O)]·2H₂O}_n, was obtained by the reaction of CuCl₂·2H₂O and 2,2′‐bipyridyl‐3,3′‐di­carboxylic acid (H₂L) in water. In the mol­ecule, each Cu^II atom is five‐coordinated and lies at the centre of a square‐pyramidal basal plane, bridged by three L ligands to form a two‐dimensional (4,4)‐network. Each L moiety acts as a bridging tetradentate ligand, coordinating to three Cu^II atoms through its two aromatic N atoms and two O atoms of the two carboxyl groups. The two‐dimensional square‐grid sheets superimpose in an off‐set fashion through the inorganic water layer.     

Bis(2,2′‐bipyridine)(dicyanamido)­copper(II) tetrafluoroborate

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂)₂]BF₄, the Cu^II atom shows distorted trigonal‐bipyramidal geometry, with the dicyan­amido ligand in the equatorial plane. The two out‐of‐plane Cu—N bond lengths to bi­pyridine are 2.006 (3) and 1.998 (3) Å, whereas the in‐plane Cu—N distances are 2.142 (3) and 2.043 (3) Å to the bi­pyridine, and 2.015 (3) Å to the dicyan­amide.     

CEC with tris(2,2′‐bipyridyl) ruthenium(II) electrochemiluminescent detection

For the first time, CEC was coupled with tris(2,2‐bipyridyl) ruthenium(II) ( Ru(bpy) electrochemiluminescence detection. Efficient CEC separations of proline, putrescine, spermidine and spermine were achieved when the pH of the mobile phase is in the range of 3.5–7.0. The optimum mobile phase for CEC separation is much less acidic than that for CZE separation, which matches better with the optimum pH for Ru(bpy) electrochemiluminescence detection and dramatically shortens the analysis time because of larger EOF at higher pH. The time for CEC separation of the polyamines is less than 12.5 min, which is about half as much as the time needed for CZE. The detection limits were 1.7, 0.2, and 0.2 μM for putrescine, spermidine, and spermine, respectively. The RSD of retention time and peak height of these polyamines were less than 0.85 and 6.1%, respectively. The column showed good long‐term stability, and the RSD of retention time is below 5% for 150 runs over one‐month use. The method was successfully used for the determination of polyamines in urine samples.     

A chloro(2‐pyridinecarboxaldehyde)(2,2′:6′,2′′‐ter­pyridine)­ruthenium(II) complex

The aldehyde moiety in the title complex, chloro(2‐pyridinecarboxaldehyde‐N,O)(2,2′:6′,2′′‐terpyridine‐κ³N)ruthenium(II)–chloro­(2‐pyridine­carboxyl­ic acid‐N,O)(2,2′:6′,2′′‐ter­pyridine‐κ³N)­ruthenium(II)–perchlorate–chloro­form–water (1.8/0.2/2/1/1), [RuCl­(C₆H₅NO)­(C₁₅H₁₁N₃)]_1.8[RuCl­(C₆H₅­NO₂)(C₁₅H₁₁N₃)]_0.2­(ClO₄)₂·­CHCl₃·­H₂O, is a structural model of substrate coordination to a transfer hydrogenation catalyst. The title complex features two independent Ru^II complex cations that display very similar distorted octahedral coordination provided by the three N atoms of the 2,2′:6′,2′′‐ter­pyridine ligand, the N and O atoms of the 2‐pyridine­carbox­aldehyde (pyCHO) ligand and a chloride ligand. One of the cation sites is disordered such that the aldehyde group is replaced by a 20 (1)% contribution from a carboxyl­ic acid group (aldehyde H replaced by carboxyl O—H). Notable dimensions in the non‐disordered complex cation are Ru—N 2.034 (2) Å and Ru—O 2.079 (2) Å to the pyCHO ligand and O—C 1.239 (4) Å for the pyCHO carbonyl group.     

Cobalt(II) and cobalt(III) complexes with 4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine

4′‐Cyanophenyl‐2,2′:6′,2′′‐terpyridine (cptpy) was employed as an N,N′,N′′‐tridentate ligand to synthesize the compounds bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(II) bis(tetrafluoridoborate) nitromethane solvate, [Co^II(C₂₂H₁₄N₄)₂](BF₄)₂·CH₃NO₂, (I), and bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(III) tris(tetrafluoridoborate) nitromethane sesquisolvate, [Co^III(C₂₂H₁₄N₄)₂](BF₄)₃·1.5CH₃NO₂, (II). In both complexes, the cobalt ions occupy a distorted octahedral geometry with two cptpy ligands in a meridional configuration. A greater distortion from octahedral geometry is observed in (I), which indicates a different steric consequence of the constrained ligand bite on the Co^II and Co^III ions. The crystal structure of (I) features an interlocked sheet motif, which differs from the one‐dimensional chain packing style present in (II). The lower dimensionality in (II) can be explained by the disturbance caused by the larger number of anions and solvent molecules involved in the crystal structure of (II). All atoms in (I) are on general positions, and the F atoms of one BF₄⁻ anion are disordered. In (II), one B atom is on an inversion center, necessitating disorder of the four attached F atoms, another B atom is on a twofold axis with ordered F atoms, and the C and N atoms of one nitromethane solvent molecule are on a twofold axis, causing disorder of the methyl H atoms. This relatively uncommon study of analogous Co^II and Co^III complexes provides a better understanding of the effects of different oxidation states on coordination geometry and crystal packing.     

Biselenienyl series. II. Synthesis and resolution of 2,2′-dinitro-3,3′-biselenienyl-4,4′-dicarboxylic acid

2,2′-Dinitro-3,3′-biselenienyl-4,4′-dicarboxylic acid (VI), the first recorded compound of the 3,3′-biselenienyl series, has been prepared and resolved into its optical antipodes by fractional crystallization of its brucine salt. On the basis of the quasi-racemate method of Fredga and the O.R.D. spectra, to the dextrorotatory acid is assigned the R configuration.     

PMR study of Cd(II) complexes with 2,2′-bipyridine

The NMR method has been used to study the structure of the complexes [Cd(bipy)]SO₄.4H₂O, [Cd(bipy)](NO₃)₂.2H₂O, [Cd(bipy)₂](NO₃)₂.$\text{1}\text{2}$H₂O and [Cd(bipy)₃](NO₃)₂.7H₂O. The influence of the central ion and of diamagnetic currents of the rings in these complexes on the PMR spectrum has been investigated. In the complexes [Cd(bipy)](NO₃)₂.2H₂O and [Cd(bipy)]SO₄.4H₂O two kinds of hydration isomers, with different PMR spectra, have been obtained.     

Diastereoselective Ion Pairing of TRISPHAT Anions and Tris(4,4′-dimethyl-2,2′-bipyridine)iron(II)

Two configurationally stable, chiral anions (TRISPHAT, 1 ) behave as efficient hosts that control the configuration of a configurationally labile iron(II ) complex as the guest with high diastereoselectivity (>96 % de) upon ion pairing. The diastereoselectivity increases with decreasing solvent polarity.     

Crystallographic report: (2,2′‐Bipyridyl)bis(ethanoldithiocarbamato)zinc(II)

Zn(meadtc)₂(2,2′‐bipy) is a ZnS₃N₂ chromophore with a distorted square pyramidal geometry. The IR band at 1002 cm^?1 and the bond valence sum value of 1.98 confirmed the monodentate dithiocarbamate in coordination. The non‐bonding Zn–S distance is 5.004(3) Å. Copyright © 2004 John Wiley & Sons, Ltd.