Spectrophotometric study on the charge transfer reaction between 2-amino-4-methylpyridine with chloranilic acid in polar solvents

Charge transfer (CT) complexes formed between 2-amino-4-methylpyridine as electron donor, chloranilic acid as electron acceptor was investigated spectrophotometrically in acetonitrile (AN), methanol (MeOH) and binary mixture of acetonitrile 50% + methanol 50% (MeOH-AN). Minimum–maximum absorbance method has been used for estimating the formation constants of the CT reactions (K_CT). Job’s method of continuous variation and photometric titration studies were used to detect the stoichiometric ratios of the formed complexes, and they showed that 1:1 complexes were produced. The molar extinction coefficient (e), oscillator strength (f), dipole moment (l), CT energy (E_CT), ionisation potential (I_P) and the dissociation energy (W) of the formed complexes were estimated; they reached acceptable values suggesting the stability of the formed CT complexes. The solid CT complexes were synthesised and characterised by elemental analyses, ¹H NMR and FTIR spectroscopies where the formed complexes included proton and electron transfer.     

Studies on labile chargetransfer complexes between o-chloranil and a series of phenols

The electron donor–acceptor (EDA) interactions between o-chloranil and a series of phenols have been studied in dioxan medium. Except for resorcinol, the EDA complexes are formed instantaneously on mixing the donor and the acceptor solutions and then they decay slowly into secondary products. In case of resorcinol, formation and decay of the EDA complex are slow and simultaneous. The kinetics of all these reactions have been studied spectrophotometrically and the formation constants of EDA complexes have been determined from kinetic data. The hν_CT values change systematically as the number and position of the –OH groups change in the aromatic ring of the phenol moiety. From the trends in the hν_CT values, the Hückel parameters (h_Ö and k_C–Ö) for the –OH group, required for a PMO calculation on phenols, have been obtained in a straightforward way and the values so obtained, viz., 1.8 and 1.0 respectively, are close to the ones (1.8 and 0.8) recommended by Streitwieser on the basis of other evidences.     

Spectroscopic studies on 3- and 5-formylsalicylic acids and their complexes with Fe(III)

The electronic absorption spectra of 3-formylsalicylic acid (3-fsa) and 5-formylsalicylic acid (5-fsa) have been studied in different pure and mixed solvents. From the pure solvent study, the Einstein transition probabilities (A_if and B_if), dipole moment (D_if), oscillator strength (F_if), life time (τ), and the molar extinction coefficient (?) of the absorption bands were determined. The hydrogen bonding and orientation energies between solute and solvent molecules have been investigated from the mixed solvent spectra. The equilibrium constants, pK_a1 and pK_a2, of the two acids have been determined spectrophotometrically and a new approximate method for pK_a1 determination is suggested. The complex formation between 3-fsa and 5-fsa and Fe³⁺ in solution has been investigated spectrophotometrically and the stoichiometric ratios of the two systems have been determined applying the continuous variation, mole-ratio and the slope ratio methods which all showed a 1:1 type of complexes.     

Benchmarking of Halogen Bond Strength in Solution with Nickel Fluorides: Bromine versus Iodine and Perfluoroaryl versus Perfluoroalkyl Donors

The energetics of halogen bond formation in solution have been investigated for a series of nickel fluoride halogen bond acceptors; trans-[NiF(2-C₅NF₄)(PEt₃)₂] ( A1 ), trans-[NiF{2-C₅NF₃(4-H)}(PEt₃)₂] ( A2 ), trans-[NiF{2-C₅NF₃(4-NMe₂)}(PEt₃)₂] ( A3 ) and trans-[NiF{2-C₅NF₂H(4-CF₃)}(PCy₃)₂] ( A4 ) with neutral organic halogen bond donors, iodopentafluorobenzene ( D1 ), 1-iodononafluorobutane ( D2 ) and bromopentafluorobenzene ( D3 ), in order to establish the significance of changes from perfluoroaryl to perfluoroalkyl donors and from iodine to bromine donors. ¹⁹F NMR titration experiments have been employed to obtain the association constants, enthalpy, and entropy for the halogen bond formed between these donor-acceptor partners in protiotoluene. For A2 – A4 , association constants of the halogen bonds formed with iodoperfluoroalkane ( D2 ) are consistently larger than those obtained for analogous complexes with the iodoperfluoroarene ( D1 ). For complexes formed with A2 – A4 , the strength of the halogen bond is significantly lowered upon modification of the halogen donor atom from I (in D1 ) to Br (in D3 ) (for D1 : 5≤K₂₈₅≤12 m ⁻¹, for D3 : 1.0≤K₁₉₃≤1.6 m ⁻¹). The presence of the electron donating NMe₂ substituent on the pyridyl ring of acceptor A3 led to an increase in −ΔH, and the association constants of the halogen bond complexes formed with D1 – D3 , compared to those formed by A1 , A2 and A4 with the same donors.     

Spectroscopic and thermodynamic studies of complexation of some divalent metal ions with isatin-<Emphasis Type="Italic">β</Emphasis>-thiosemicarbazone

Metal complexes of some divalent metal ions (Co, Ni, Cu, Zn, Hg, and Pd) with isatin-β-thiosemicarbazone (ITS) as the Schiff base have been investigated potentiometrically and spectrophotometrically. The dissociation constants of the ligand and formation constants of the metal complexes, as well as the corresponding thermodynamic functions (ΔG, ΔH and ΔS) have been determined at different temperatures in ethanol—water solution. The full stability constants were also evaluated spectrophotometrically by the Job method. The experimental results indicate that Cu(II), Zn(II), Pd(II), and Hg(II) form one-to-one molecular complexes (ML) with the studied ligand, whereas Co(II) and Ni(II) form both ML and ML₂ species.     

Stability,spectra and structure of the cobalt(II) chloride complexes in hexamethylphosphoramide solution at 25°C

Cobalt(II) chloride complexes were investigated spectrophotometrically in hexamethylphosphoramide (HMPA) solutions. It has been established that four consecutive tetrahedral chloro complexes of cobalt(II) are formed in the Co(ClO₄)₂-CoCl₂ and CoCl₂-LiCl-HMPA solutions. The formation constants of the complexes have been calculated: log K₁ = 9.0 (±0.5), log K₂ = 6.5 (±0.5), log K₃ = 3.05 (±0.05) and log K₄ = − 1.42 (±0.03). The high stability of the dichloro-complex results in the fact that this species is the only complex of cobalt(II) existing in HMPA solutions of CoCl₂.     

Coenzyme B12 model studies: An HSAB approach to the equilibria and kinetics of axial ligation of alkyl(aquo)-cobaloximes by imidazole and cyanide

Kinetics and equilibria of the axial ligation of alkyl(aquo)cobaloximes by imidazole and cyanide have been measured spectrophotometrically in aqueous solutions of ionic strength 1.0 M at 25°C as a function of pH. Comparison of K_IMD and K_CN- of CH₃, C₂H₅ and BrCH₂cobaloximes indicates that their stability is in the order BrCH₂>CH₃>C₂H₂. As the electron-withdrawing capacity of the alkyl grouptrans to water increases, the electron density of the cobalt(III) decreases and thus it becomes a stronger Lewis acid and binds more strongly to imidazole and cyanide. The association and dissociation rate constants are better correlated to the relative softness of the ligand showing that cyanide binds 30 times faster than imidazole. These complexes are isolated and are characterized by IR and¹H NMR spectra.     

The electronic effect in supramolecular self-assembly of <Emphasis Type="Italic">para-</Emphasis>substituted tetraphenylporphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) by coordinative bonding

The supramolecular self-assembly of para-substituted tetraphenylporphyrin complexes of zinc(II), Zn(p-X)TPP, with imidazolyl-linked porphyrinatomanganese(III), Mn(p-lmBPTPP)Cl, driven by coordinative bonding has been investigated by fluorescence spectra, electrospray mass spectrometry, ¹H-n.m.r. and u.v.–vis. spectra. The association constants of the supramolecular complexes, K_c, were calculated using fluorescence spectroscopic titration data at suitable dilute concentration ranges in which the fluorescent quenching of Zn(p-X)TPP by Mn(p-ImBPTPP)Cl is a static process. The electronic effect in the supramolecular self-assembly of para-substituted . porphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) is discussed. The non-linear dependence of log K_c on the Hammett constants was found, which suggested that the electronic effect in para-substituents of tetraphenylporphyrin complexes of zinc(II) is an important, but not a sole factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes. The results indicate that the closed conformation of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complex is another important factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes.     

Spectroscopic studies of intermolecular hydrogen bonding and proton transfer complexes of chromotropic acid with some amines in methanol

The proton transfer reactions between chromotropic acid (CTA) and some amines including benzylamine (BA), triethylamine (TEA), pyrrolidine (PY) and 1,8-bis(dimethylamino) naphthalene (DMAN) have been investigated spectrophotometrically in methanol. A long wavelength band at 365 nm has been recorded due to the proton transfer (PT) complex formation. The proton transfer equilibrium constants K_PT were estimated utilizing the minimum–maximum absorbances method. It has been found that K_PT were not depend on the amine pKa values, but strongly depend on the formed structures of the PT complexes. Job^’s method of continuous variations and photometric titrations were applied to identify the compositions of the formed PT complexes where 1:1 complexes (proton donor: proton acceptor) were produced. Due to the rapidity and simplicity of the proton transfer reactions and the stability of the formed complexes, a rapid and accurate spectrophotometric method for the determination of CTA was proposed for the first time.     

Laws of complex formation in a series of azo-substituted pyrocatechol derivatives and their tin(II) complexes

Physicochemical properties of new reagents, azo-substituted pyrocatechol derivatives and their tin(II) complexes, are studied. The acid-base properties of the hydroxy groups (pK′_i, pK″_i), parameters of complex formation reactions (pH, temperature, time), and instability constants of the complexes formed (pK _i) are determined. Quantitative correlations between the dissociation constants (pK′_a) of the functional analytical group, and the electronic Hammett constant σ for a substituent (pK′_a-pH₅₀ of the complex formation reaction), as well as between pK′_a and instability constants of the complexes (pK _a), are established. The quantitative correlations established allow the prediction of the physicochemical properties of the reagents and tin(II) complexes with new reagents of this class with the same functional analytical group (FAG) but other substituents.     

Lewis Acids as Activators in CBS‐Catalysed Diels–Alder Reactions: Distortion Induced Lewis Acidity Enhancement of SnCl4

The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While ²H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT‐IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ(²H) values and rate constants k_DA, which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid–CBS complexes. Unexpectedly, a significant deviation was found for SnCl₄ as Lewis acid. The SnCl₄–CBS adduct was much more reactive than the Δδ(²H) values predicted and gave similar reaction rates to those observed for the prominent AlBr₃–CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid–CBS–naphthoquinone adducts and k_DA could be found. For the SnCl₄–CBS–naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA‐NOCV) calculations revealed the relevant interactions and activation mode of SnCl₄ as Lewis acid in Diels–Alder reactions.     

Acid-base and complexing properties of 10-carboxymethyl-9-acridone

Acid-base and complexing properties of 10-carboxymethyl-9-acridone in a multicomponent solvent H₂O-methanol-acetonitrile-dioxane were studied at 22°C, ionic strength I = 0.1 (NaClO₄), and different water-organic component ratios. The concentration protonation constants (logK _HL = 3.11), dissociation constants (pK _HL = 4.14), and stability constants of complexes (logK _MgL = 2.18, logK _CaL = 2.09, and logK _SrL = 1.96) were determined by extrapolation to zero content of organic solvent.     

Facilitated Transfer of Alkali Metal Ions by a Tetraester Derivative of Thiacalix[4]arene at the Liquid–Liquid Interface

The facilitated transfer of alkali metal ions (Na⁺, K⁺, Rb⁺, and Cs⁺) by 25,26,27,28‐tetraethoxycarbonylmethoxy‐thiacalix[4]arene across the water/1,2‐dichloroethane interface was investigated by cyclic voltammetry. The dependence of the half‐wave transfer potential on the metal and ligand concentrations was used to formulate the stoichiometric ratio and to evaluate the association constants of the complexes formed between ionophore and metal ions. While the facilitated transfer of Li⁺ ion was not observed across the water/1,2‐dichloroethane interface, the facilitated transfers were observed by formation of 1 : 1 (metal:ionophore) complex for Na⁺, K⁺, and Rb⁺ ions except for Cs⁺ ion. In the case of Cs⁺ a 1 : 2 (metal:ionophore) complex was obtained from its special electrochemical response to the variation of ligand concentrations in the organic phase. The logarithms of the complex association constants, for facilitated transfer of Na⁺, K⁺, Rb⁺, and Cs⁺, were estimated as 6.52, 7.75, 7.91 (log β₁°), and 8.36 (log β₂°), respectively.     

Study of Electron Donor–Acceptor Complex Formation of o-Chloranil With a Series of Phosphine Oxides and Tri- n-butyl Phosphate by the Absorption Spectrometric Method

Electron donor–acceptor (EDA) complex formation of o-chloranil with six different phosphine oxides and tri-n-butyl phosphate (TBP) has been studied in CCl ₄ solution by the UV-VIS absorption spectrophotometric technique. An absorption band due to a charge–transfer (CT) transition is observed in the visible region. Utilizing the CT transition energy, the electron affinity of o-chloranil in solution has been calculated. Degrees of charge transfer, and oscillator and transition dipole strengths have also been calculated for all of the investigated EDA complexes. Except for TBP, other phosphine oxides, viz., tri-n-octyl phosphine oxide, tri-n-butyl phosphine oxide, triphenyl phosphine, octyl(phenyl)-N,N-diisobutylcarbamoylphosphine oxide, octyl(phenyl)-N,N-dicyclohexylcarbamoylmethylphosphine oxide and octyl(phenyl)-N,N-diisopropylcarbamoylmethylphosphine oxide have been shown to form stable 1:1 EDA complexes with o-chloranil. The complex of TBP with o-chloranil decays slowly into a secondary product. Formation constants of the EDA complexes have been determined.     

Spectroscopic study of the complexation of an aza-15-crown-5 containing chromofluoroionophore with Ba2+ and Ca2+ cations

The complexation of 1-[(4-benzothiazolyl)phenyl]-4,7,10,13-tetraoxa-1-aza-cyclopenta-decane with Ba²⁺ and Ca²⁺ cations was investigated spectrophotometrically and spectrofluorometrically. The stability constants of the complexes formed are: for Ba²⁺ logK _st=3.17±0.01 (absorption) and logK _st=2.95±0.03 (fluorescence); for Ca²⁺ logK _st=3.71±0.02 (absorption) and logK _st=3.58±0.05 (fluorescence). Protonation of the ligand leads to fluorescence quenching. AM1 and PPP quantum chemical calculations were used to predict molecular geometry, proton affinities and the spectra of the compounds studied.Dedicated to Prof. Dr. Karl-Heinz Drexhage on the occasion of his 60th birthday     

Interaction of Iodine with Hexaaza-18-crown-6 and Tetraaza-14-crown-4 in Chloroform Solution

Interactions of hexaaza-18-crown-6 (HA18C6) and tetraaza-14-crown-4 (TA14C4) with iodine have been investigated spectrophotometrically in chloroform solution. The observed time dependence of the charge-transfer band and subsequent formation of I₃ ^- in solution were related to the slow transformation of the initially formed 1:1 macrocycle. I₂ outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows: macrocycle + I₂→_fast ^K _f macrocycle.I₂ (outer complex) macrocycle.I₂ (outer complex) →^slow (macrocycle.I⁺)I^- (inner complex) macrocycle.I⁺)I^- (inner complex) + I²→^slow (macrocycle.I⁺)I₃ ^-. The pseudo-first-order rate constants at various temperatures for thetransformation process were evaluated from the absorbance-time data. The activation parameters (E_a, Δ H^?, and Δ S^?) for thetransformation were obtained from the temperature dependence of the rate constants. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. It was found that the (TA14C4.I⁺)I₃ ^- is more stable the (HA18C6.I⁺)I₃ ^- complex in chloroform solution.     

The Stabilities of the o-Carboxyphenylhydrazo-Ethylacetoacetate OF Cu,Ni, Co,Zn, Mn and Cd Chelate Compounds in Different Solvents

The dissociation constants for o-carboxyphenylhydrazoethylacetoacetate (o-CPHEA) ligand, as well as the stability constants for the divalent metal complexes of Cu, (II), Ni (II), Co (II), Zn (II)and Cd (II) ions, have been calculated pH-meterically in different solvents. The dissociation constans pK₁=4.10 and pK₂=10.55 of the insoluble organic ligand are calculated in aqueous medium. The effect of solvents, the relation between stabilities and both electronegativities and ionization potential are studied.     

Formation of mercury(ii) ethylenediaminediacetate and its mixed-ligand complexes with anions

The complexes of mercury(II) with EDDA and the formation of mixedligand complexes with some anions have been investigated spectrophotometrically. Mercury(II) reacts with EDDA to give 1:1 and 1:2 complexes, which have stability constants of 15.4±0.1 and 24.2±0.2 respectively, at ionic strength 0.1. These complexes react with anions (X), such as cyanide, thiocyanate, iodide, bromide and chloride, to form the mixed-ligand 1:1:1 complexes. Hg(EDDA)X. The apparent stability constants (log K_x) of the chloro, bromo, and thiocyanato mixed-ligand complexes are 9.9, 12.0, and 10.8, respectively.     

Chelate Compounds of a Selected Non-Transition and Transition Metal Ions with Some Salicylic Acid Derivatives

A series of binary complexes of Zn(II), Hg(II), Pb(II), La(III), Ce(III), Th(IV) and UO₂(II) with 3,5-dinitrosalicylic acid and 5-sulphosalicylic acid have been isolated and characterized. The solution equilibria of these complexes have been studied pH-metrically. The formation constants (log K) at 25±1°C and ionic strength of 0.2M NaClC₄ have been calculated. Stability of the complexes formed in relation to ligand molecular structure and nature of the metal ion has been examined and discussed.