Rate constants and activation parameters for organo-cobalt porphyrin bond homolysis from NMR relaxation times

¹H NMR line broadening is found to be an effective complimentary method to chemical trapping for determining the rates and activation parameters for organo-metal bond homolysis events that produce freely diffusing radicals. Application of this method is illustrated by measurement of bond homolysis activation parameters for a series of organo-cobalt porphyrin complexes ((TPP)Co-C(CH₃)₂CN (ΔH^≠ = 19.5±0.9 kcal mol⁻¹, ΔS^≠ = 12±3 cal°K⁻¹ mol⁻¹), (TMP)Co-C(CH₃)₂CN (ΔH^≠ = 20±1 kcal mol⁻¹,ΔS^≠ = 13±2 cal°K⁻¹ mol⁻¹), (TAP)Co-C(CH₃)₂CO₂CH₃ (ΔH^≠ = 18.2±0.5 kcal mol⁻¹, ΔS^≠ = 12±2 cal °K⁻¹ mol⁻¹), (TAP)Co-CH(CH₃)C₆H₅ (ΔH^≠ = 22.5±0.5, ΔS^≠ = 17±2 cal °K⁻¹ mol⁻¹)). The line broadening method is particularly useful in determining activation parameters for dissociation of weakly bonded organometallics where the rate of homolysis can exceed the range measurable by conventional chemical trapping methods.     

The dynamics of formation of the O2-Co bond in the cobalt(II) cyclidene complexes

The kinetics of O₂ binding to a vacant coordination site on the cobalt(II) ion have been determined, revealing a radical-like character for the reaction. Reversible oxygenation of Co(II) cyclidenes (C4, C5, C6, C8, C12-bridged and unbridged) was studied by a cryogenic stopped-flow method. In the presence of axial base, kinetic parameters are insensitive to the nature of the solvent, and negative entropies of activation suggest that dissociation of a solvent molecule is not the rate-determining step for the dioxygen binding process. This is in contrast to the behavior of previously studied Co(II) complexes. A very low activation energy (1–4 kcal mol⁻¹), typical of diffusion controlled processes, was found for dioxygen binding. The binding rate constants for the highest affinity complexes (10⁸ M⁻¹ s⁻¹) are comparable to the values for natural dioxygen carriers. The size of the lacuna primarily affects the dioxygen binding rates, while the axial bases influence the dioxygen dissociation rates.     

Kinetics and mechanism of the stoichiometric oxygenation of [Cu(fla)(idpa)]ClO4 [fla=flavonolate, IDPA=3,3′-imino-bis(N,N-dimethylpropylamine)] and the [Cu(fla)(idpa)]ClO4-catalysed oxygenation of flavonol

Oxygenation of [Cu^II(fla)(idpa)]ClO₄ (fla=flavonolate; IDPA=3,3′-iminobis(N,N-dimethylpropylamine)) in dimethylformamide gives [Cu^II(idpa)(O-bs)]ClO₄ (O-bs=O-benzoylsalicylate) and CO. The oxygenolysis of [Cu^II(fla)(idpa)]ClO₄ in DMF was followed by electronic spectroscopy and the rate law −d[{Cu^II(fla)(idpa)}ClO₄]/dt=k_obs[{Cu^II(fla)(idpa)}ClO₄][O₂] was obtained. The rate constant, activation enthalpy and entropy at 373 K are k_obs=6.13±0.16×10⁻³ M⁻¹ s⁻¹, ΔH^‡=64±5 kJ mol⁻¹, ΔS^‡=−120±13 J mol⁻¹ K⁻¹, respectively. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper gives faster oxygenation rates. The complex [Cu^II(fla)(idpa)]ClO₄ has also been found to be a selective catalyst for the oxygenation of flavonol to the corresponding O-benzoylsalicylic acid and CO. The kinetics of the oxygenolysis in DMF was followed by electronic spectroscopy and the following rate law was obtained: −d[flaH]/dt=k_obs[{Cu^II(fla)(idpa)}ClO₄][O₂]. The rate constant, activation enthalpy and entropy at 403 K are k_obs=4.22±0.15×10⁻² M⁻¹ s⁻¹, ΔH^‡=71±6 kJ mol⁻¹, ΔS^‡=−97±15 J mol⁻¹ K⁻¹, respectively.     

Temperature dependence study of five-coordinate complex formation of zinc(II) octaethyl and tetraphenylporphyrin

Five coordinate complex formation of zinc(II)–octaethylporphyrin (Zn(OEP)) and zinc(II)–tetraphenylporphyrin (Zn(TPP)) have been studied in the presence of seven systematically selected electron donor molecules. Stability constants in toluene were determined at various temperature ranged between 20 and 60°C by absorption and steady-state fluorescent measurements from which thermodynamic parameters were determined. Depending on the porphyrin and the axial ligand the entropy is changing between −127 and −61 J mol⁻¹ K⁻¹ while the enthalpy is ranging from −49 to −24 kJ mol⁻¹.     

Model reactions of a carbonylation catalyst: phosphite induced migratory CO insertion in [MeIr(CO)2I3]

Carbonylation of the anionic iridium(III) methyl complex, [MeIr(CO)₂I₃]⁻ (1) is an important step in the new iridium-based process for acetic acid manufacture. A model study of the migratory insertion reactions of 1 with P-donor ligands is reported. Complex 1 reacts with phosphites to give neutral acetyl complexes, [Ir(COMe)(CO)I₂L₂] (L = P(OPh)₃ (2), P(OMe)₃ (3)). Complex 2 has been isolated and fully characterised from the reaction of Ph₄As[MeIr(CO)₂I₃] with AgBF₄ and P(OPh)₃; comparison of spectroscopic properties suggests an analogous formulation for 3. IR and ³¹P NMR spectroscopy indicate initial formation of unstable isomers of 2 which isomerise to the thermodynamic product with trans phosphite ligands. Kinetic measurements for the reactions of 1 with phosphites in CH₂Cl₂ show first order dependence on [1], only when the reactions are carried out in the presence of excess iodide. The rates exhibit a saturation dependence on [L] and are inhibited by iodide. The reactions are accelerated by addition of alcohols (e.g. 18× enhancement for L = P (OMe)₃ in 1:3 MeOH-CH₂Cl₂). A reaction mechanism is proposed which involves substitution of an iodide ligand by phosphite, prior to migratory CO insertion. The observed rate constants fit well to a rate law derived from this mechanism. Analysis of the kinetic data shows that k₁, the rate constant for iodide dissociation, is independent of L, but is increased by a factor of 18 on adding 25% MeOH to CH₂Cl₂. Activation parameters for the k₁ step are ΔH^≠ = 71 (±3) kJ mol⁻, ΔS^≠ = −81 (±9) J mol⁻¹ K⁻¹ in CH₂Cl₂ and ΔH^≠ = 60(±4) kJ mol⁻¹, ΔS^≠ = −93(± 12) J mol⁻¹ K⁻¹ in 1:3 MeOH-CH₂Cl₂. Solvent assistance of the iodide dissociation step gives the observed rate enhancement in protic solvents. The mechanism is similar to that proposed for the carbonylation of 1.     

Pressure effects on the rates of Hg-assisted chloride release from some [CrCl(diamine)(triamine)] complexes

The rate of Hg²⁺-assisted chloride release from several mer-[CrCl(diamine)(triamine)]²⁺ complexes has been measured as a function of pressure, Hg²⁺ concentration and temperature. The calculated activation volumes are independent of [Hg²⁺] and temperature and kinetic parametes 10⁴ k_Hg (25 °c) (M⁻¹ s⁻¹), ΔH^‡ (kJ mol⁻¹), ΔS^‡ (J K⁻¹ mol⁻¹), ΔV^‡ (cc mol⁻¹) are: (en)(dpt): 6.44. 75.5, −52, −5.0; (ibn)(dpt): 5.81, 89.5, −6, −0.03; (Me₂tn)(dpt): 22.2, 84.9, −11, −0.5; (tn)(dpt): 29.1, 87, −1, +0.3; (en)(2,3-tri): 1.94, 87.0, −24, −5.7; (en)(Medpt): 0.417, 94.6, −11, −0.8; (tn)(Medpt): 9.14, 98.3, +26, +1.8.     

The kinetics and energetics of formation of a molecular hydrogen complex involving a dinuclear ruthenium(II) centre

The reversible equilibrium conversion under H₂ of [RuCl(dppb) (μ-Cl)]₂ (1) to generate (η²-H₂) (dppb) (μ-Cl)₃RuCl(dppb) in CH₂Cl₂ (dppb = Ph₂P(CH₂)₄PPh₂) has been studied at 0–25 °C by UV-Vis and ³¹P{¹H} NMR spectroscopy, and by stoppe kinetics; the equilibrium constant and corresponding thermodynamic parameters, and the forward and reverse rate constants at 25 °C have been determined. A measured ΔH° value of 0 kJ mol⁻¹ allows for an estimation of an exothermicity of 60 kJ mol⁻¹ for binding an η²-H₂ at an Ru(II) centre; a ΔS° value of 60 J mol⁻¹ K⁻¹ indicates that in solution 1 contain s coordinated CH₂Cl₂. The kinetic and thermodynamic data are compared to those obtained from a previously studied hydrogenation of styrene catalyzed by 1. Preliminary findings on related systems containing Ph₂P(CH₂)₃PPh₂ and (C₆H₁₁)₂P(C₆H₁₁)₂ are also noted.     

Kinetics and mechanism of the axial substitution reactions of (ligand)bis(4,5-dichloro-1,2-benzo semiquinonediiminato)cobalt(III) complexes

Square-pyramidal (Ph₃X)bis(4,5-dichloro-1,2-benzosemiquinonediiminato)cobalt(III) complexes (X = As, Sb or P) have been synthesized. The kinetics of axial substitution for the triphenylantimony complex have been studied for 10 entering ligands (L*). The reaction is of reversible second-order in both directions for all complexes. Labile behavior is indicated by the rate constants in the range from 6.33 × 10³ (for L* = Ph₃P in MeOH) to 5.4 (L* = py in CH₂Cl₂) M⁻¹ s⁻¹. The kinetics is consistent with an I_a mechanism. The log of the second-order rate constant for axial substitution is a linear function of nucleophilic reactivity n_Pt°, which is due to the trans-labilizing effect of the entering ligand in the six-coordinate transition state.     

Ricochet inter-ring haptotropic rearrangement of σ-methyl-(η-indenyl) chromium tricarbonyls. Experimental kinetic and theoretical DFT study

σ-Methyl-(η⁵-indenyl) chromium tricarbonyl (III) rearranges quantitatively into η⁶-1-endo-methylindene) chromium tricarbonyl (IV) in C₆D₆ solution at 30–60°C. Methyl group attachment to the positions 2 or 3 of indenyl ligand in (III) has no influence on the activation parameters of this ricochet inter-ring haptotropic rearrangement (ΔG^#=23.6 kcal mol⁻¹; ΔH^#=18.9±0.2 kcal mol⁻¹; ΔS^#=−18.6±0.2 cal K⁻¹ mol⁻¹). (IV) undergoes further irreversible isomerization at 60–120° into (ν⁶-3-methylindene) chromium tricarbonyl (V) with a higher activation barrier (ΔG^#=28.5±0.1 kcal mol⁻¹) via two consecutive [1,5]-sigmatropic hydrogen shifts. The mechanisms of both rearrangements have been studied in detail using density functional theory (DFT) calculations with extended basis sets. Calculations show that the rearrangement (III) → (IV) proceeds in two steps. Methyl group migration from chromium into position 1 of the indenyl ligand is the rate-determining step leading to the formation of the 16-electron intermediate (VII). The calculated activation barrier (E_a=19.6 kcal mol⁻¹) is in good agreement with the experimental one. Further rearrangement (VII) → (V) proceeds via a trimethylenemethane-type transition state (XVIII) with an activation barrier 11.8 kcal mol⁻¹. The coordination of the chromium tricarbonyl group at the six-membered ring has only minor influence on the kinetic parameters of the hydrogen [1,5]-sigmatropic shift in indene.     

Nickel(II) and copper(II) complexes of mixed benzene-triazolehemiporphyrazines

The kinetics of substitution reactions of [η-CpFe(CO)₃]PF₆ with PPh₃ in the presence of R-PyOs have been studied. For all the R-PyOs (R = 4-OMe, 4-Me, 3,4-(CH)₄, 4-Ph, 3-Me, 2,3-(CH)₄, 2,6-Me₂, 2-Me), the reactions yeild the same product [η⁵-CpFe(CO)₂PPh₃]PF₆, according to a second-order rate law that is first order in concentrations of [η⁵-CpFe(CO)₃]PF₆ and of R-PyO but zero order in PPh₃ concentration. These results, along with the dependence of the reaction rate on the nature of R-PyO, are consistent with an associative mechanism. Activation parameters further support the bimmolecular nature of the reactions: ΔH^≠ = 13.4 ± 0.4 kcal mol⁻¹, ΔS^≠ = −19.1 ± 1.3 cal k⁻¹ mol⁻¹ for 4-PhPyO; ΔH^≠ = 12.3 ± 0.3 kcal mol⁻¹, ΔS^≠ = 24.7 ±1.0 cal K⁻¹ mol⁻¹ for 2-MePyO. For the various substituted pyridine N-oxides studied in this paper, the rates of reaction increase with the increasing electron-donating abilities of the substituents on the pyridine ring or N-oxide basicities, but decrease with increasing ¹⁷O chemical shifts of the N-oxides. Electronic and steric factors contributing to the reactivity of pyridine N-oxides have been quantitatively assessed.     

Heats of reaction of HMo(CO)3(C5R5) (R = H, CH3) with diphenyldisulfide and of formation of the clusters [PhSMo(CO)x(C5H5)]2, X = 1,2. Thermodynamic study of molybdenum-sulfur bond strengths

The enthalpies of reaction of HMo(CO)₃C₅R₅ (R = H, CH₃) with diphenyldisulfide producing PhSMo(CO)₃C₅R₅ and PhSH have been measured in toluene and THF solution (R = H, ΔH= −8.5 ± 0.5 kcal mol⁻¹ (tol), −10.8 ± 0.7 kcal mol⁻¹ (THF); R = CH₃, ΔH = −11.3±0.3 kcal mol⁻¹ (tol), −13.2±0.7 kcal mol⁻¹ (THF)). These data are used to estimate the Mo---SPh bond strength to be on the order of 38–41 kcal mol⁻¹ for these complexes. The increased exothermicity of oxidative addition of disulfide in THF versus toluene is attributed to hydrogen bonding between thiophenol produced in the reaction and THF. This was confirmed by measurement of the heat of solution of thiophenol in toluene and THF. Differential scanning calorimetry as well as high temperature calorimetry have been performed on the dimerization and subsequent decarbonylation reactions of PhSMo(CO)₃Cp yielding [PhSMo(CO)₂Cp]₂ and [PhSMo(CO)Cp]₂. The enthalpies of reaction of PhSMo(CO)₃Cp and [PhSMo(CO)₂Cp]₂ with PPh₃, PPh₂Me and P(OMe)₃ have also been measured. The disproportionation reaction: 2[PhSMo(CO)₂Cp]₂ → 2PhSMo(CO)₃Cp + [PhSMP(CO)Cp]₂ is reported and its enthalpy has also been measured. These data allow determination of the enthalpy of formation of the metal-sulfur clusters [PhSMo(CO)_nC₅H₅]₂, N = 1,2.     

The migratory insertion of carbon monoxide in pentamethylcyclopentadienyliridium (III) complexes. Structural effects on reactivity and mechanism for rhodium and iridium systems

The reactions of complex (C₅Me₅)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh₂, PMePh₂, PMe₂Ph) give the products of alkyl migratory insertion (C₅Me₅Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C₅Me₅)Ir(Cl)(CO)(Ph) or the iodide complexes (C₅Me₅)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C₅Me₅)Ir(Cl)(CO)(Me) with PMePh₂ and PMe₂Ph in acetonitrile yields the chloride substitution product [(C₅Me₅)Ir(CO)(L)(Me)]⁺Cl⁻. Kinetic measurements for the reactions of (C₅Me₅)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C₅Me₅)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step (K = 1.5 (CyNC), 7.3 (PHPh₂), 7.1 (PMePh₂) dm³ mol⁻¹ at 323 K) and k₂ for the slow carbon---carbon bond formation (k₂ (10⁵) = 6.9 (CyNC), 1.2 (PHPh₂), 1.0 (PMePh₂) s⁻¹ at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh₂ obtained between 308 and 338 K, are ΔH^≠ = 106±16 kJ mol⁻¹ and ΔS^≠ = − 14±5 J K⁻¹ mol⁻¹. The reaction of 1a with PMePh₂ proceeds at similar rates in tetrahydrofuran (K = 3.7 dm³ mol⁻¹, k₂ (10⁵) = 1.2 s⁻¹, 323 K). The crystal structure of (C₅Me₅)Ir(Cl)(COMe) (PMe₂Ph) has been determined by X-ray diffraction. C₂₀H₂₉ClOPIr: M_r = 544.1, monoclinic, P2₁/n, A = 8.084 (2), B = 9.030(2), C = 28.715 (3) Å, β = 91.41 (3)°, Z = 4, D_c = 1.71 g cm⁻³, V = 2095.5 ų, room temperatyre, Mo K, γ = 0.71069, μ = 65.55 cm⁻¹, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η⁵-C₅Me₅ molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the Ir---P and the Ir---COMe bonds are eclipsed with respect to C(ring)-methyl bonds.     

Experimental and theoretical study of a truly functional biomimetic molybdenum oxotransferase analogue system

Density functional theory (DFT) computations at the B3LYP/Lanl2DZ level were used to elucidate the oxygen atom transfer (OAT) and coupled electron proton transfer (CEPT) reaction steps involved in the biomimetic catalytic cycle performed by polymer-supported Mo^VIO₂(NN′)₂ complexes [NN′ = phenyl-(pyrrolato-2-ylmethylene)-amine] with water as oxygen source, trimethyl-phosphane as oxygen acceptor and one-electron oxidising agents. The DFT method employed has been validated against experimental data [X-ray crystal structures of a NN′ ligand and a Mo^VIO₂(NN′)₂ complex as well as kinetic data]. The rate-limiting step in the forward-OAT from [Mo^VIO₂] to PMe₃ is the attack of PMe₃ at an oxo ligand with ΔG^≠ (298 K) = 64.6 kJ mol⁻¹. Dissociation of the product OPMe₃ is facile with ΔG^≠ (298 K) = 26.3 kJ mol⁻¹ giving a mono-oxo [Mo^IVO] complex which fills its coordination sphere with a further PMe₃ substrate with ΔG^≠ (298 K) = 39.2 kJ mol⁻¹. One-electron oxidation to a Mo(V) phosphane complex precedes the coordination of water/hydroxide. Additionally, the comproportionation of [Mo^VIO₂] and [Mo^IVO] to dinuclear oxo-bridged [OMo^V–O–Mo^VO] species has been calculated as the thermodynamic sink in this system and the back-OAT from dmso to mono-oxo [Mo^IVO] to give [Mo^VIO₂] has been shown to involve an equilibrium between stereoisomeric [Mo^VIO₂] complexes with an activation barrier of ΔG^≠ (298 K) = 113.1 kJ mol⁻¹.     

Proton nuclear magnetic resonance study of N,N-diethylformamide exchange on (N,N-diethylformamide)2,2′2″-tris(dimethylamino)triethylamine)cobalt(II) and its copper(II) analogue

Proton NMR studies of N,N-diethylformamide (def) exchange on [M(Me₆tren)def]²⁺ where M = Co and Cu yield: k_ex (298.2K) = 26.3 ± 2.2, 980 ± 70 s⁻¹; ΔH^≠ = 58.3 ± 1.7, 36.3 ± 0.9 kJ mol⁻¹; ΔS^≠= −22.2 ± 4.6, −65.9 ± 2.5 J K⁻¹ mol⁻¹; and ΔV^≠ = −1.3 ± 0.2, 5.3 ± 0.3 cm³ mol⁻¹ respectively. These data which are consistent with a and d activation modes operating when M = Co and Cu respectively are compared with data for related systems.     

Kinetics of adsorption of Zn(II) ion on chitosan derivatives

The adsorption of Zn(II) ions from aqueous solution by chitosan derivatives (KCTS and HKCTS) was studied in a batch adsorption system. The adsorption capacities and rates of Zn(II) ions onto chitosan derivatives were evaluated. The adsorption isothermal data could be well interpreted by the Langmuir and Freundlich models. The kinetic experimental data properly correlated with the second-order kinetic model, which indicates that the chemical adsorption is the rate-limiting step. The apparent adsorption activation energy were 25.47 kJ mol⁻ and 5.473 kJ mol⁻, respectively, and the second-order adsorption constant for KCTS and HKCTS were 0.00311 g (mg min)⁻¹ and 0.005 g (mg min)⁻¹, respectively.     

Reaction of nitric oxide with iron bleomycin bound to DNA: properties of the nitrosyl adduct and its reaction with O2

During the ESR spectroscopic titration of nitrosyl-iron bleomycin, ON---Fe(II)Blm, with DNA, its metal domain undergoes a change in environment as the DNA base pair to drug ratio increases to 50 to 1. The ¹⁵N---O stretching frequency of ON---Fe(II)Blm occurs at 1589 cm⁻¹, similar to that for nitrosyl hemoglobin and myoglobin. Upon addition of DNA (3 base pairs per drug molecule), this vibration is substantially broadened. Injection of O₂ into a solution of ON---Fe(II)BlmDNA converts the ESR signal of the nitrosyl species to low spin Fe(III) BlmDNA. NO is largely oxidized to NO₂⁻. The combination of these products suggests that the initial reaction of ON---Fe(II)Blm with O₂ generates Fe(III)Blm and peroxynitrite, O₂NO⁻. If peroxynitrite is formed in the reaction, it does not cause detectable DNA damage. The structural integrity of a supercoiled DNA plasmid, pBR322, is not compromised and no base propenals are produced during this reaction.     

Syntheses, characterisation, infrared and Mo NMR spectroscopy of some coordinated oxo—molybdenum(VI) complexes

Adducts with MoO₄²⁻ tetrahedra coordinated to Cr(III) or Co(III) complexes have been synthesized and studied by IR and high resolution ⁹⁵Mo NMR spectroscopy. The ⁹⁵Mo chemical shifts of the adducts with cobalt(III) lie in the range −33.2 to + 49.4 ppm. This may be compared with an overall known chemical shift range in excess of 7000 ppm and implies a similarity in the molybdenum environment in all cases. For adducts with chelated cobalt(III) complexes several rather broad ⁹⁵Mo singnals are obtained with linewidths up to 260 Hz.     

Syntheses, structures and magnetic properties of mono- and di-manganese inclusion compounds

Mono- and di-manganese inclusion compounds 1 and 2 are reported. Two mono-manganese molecules Mn(bpy)₂(NO₃)₂ (bpy=2,2′-bipyridine) and [Mn(bpy)₂(NO₃)(H₂O)]·NO₃ coexist in the mole ratio of 1:1 in the structure of 1, while two di-manganese molecules [Mn₂O(bpy)₂(phtha)₂(H₂O)₂]·(NO₃)₂ (phtha=phthalate) and [Mn₂O(bpy)₂(phtha)₂(NO₃)(H₂O)]·NO₃ in the structure of 2. Refluxing Mn(NO₃)₂/bpy/phthalic acid reaction mixtures in CH₃CN leads to the isolation of 1, further concentration of the reaction solution in raising temperature results in 2. The Mn₁ and Mn₂ units in the inclusion compounds 1 and 2 are similar to other reported Mn₁ and Mn₂ analogs, respectively. The Jahn–Teller distortion was observed to give rise to the elongation along the O_terminal---Mn---O_carboxyl axes for all the four Mn(III) sites in 2, leading to unexpected longer Mn(III)---O_aqua than Mn(II)---O_aqua in 1. Extensive hydrogen bonding interactions among H₂O, NO₃ ⁻ and COOH were observed in the two inclusion compounds. Cyclic voltammetry of 2 in DMF displays two quasi-reversible redox couples at +0.10/+0.22 and −0.43/−0.36 V assigned to the Mn(III)Mn(IV)/2Mn(III) and 2Mn(III)/Mn(III)Mn(II), respectively. Variable temperature magnetic susceptibilities of 1 and 2 were measured. The data were fit to a model including axial zero-field splitting term and a good fit was found with D=1.77 cm⁻¹, g=1.98 and F=1.48×10⁻⁵ for 1. For 2, the least-squares fitting of the experimental data led to J=2.37 cm⁻¹, g=2.02 and D=0.75 cm⁻¹ with R=1.45×10⁻³.     

Electronic absorption spectroscopy for the investigation of the solution binding of gold, palladium, mercury and silver salts to the lower rim substituted calix[4]arenes 25,26,27,28-(2-N,N-dimethyldithiocarbamoylethoxy)calix[4]arene and 25,26,27,28-(2-methylthioethoxy)calix[4]arene

The two uncharged compounds 25,26,27,28-(2-N,N-di methyldithiocarbamoylethoxy)calix[4]arene (1) and 25,26,27,28- (2-methylthioethoxy)calix[4]arene (2) are effective extractants for transferring Hg(II), Ag(I), Pd(II) and Au(III) from aqueous solution into chloroform. The electronic absorption spectra of 1 and 2 show additional bands at long wavelength upon complexation with AuCl₄⁻, PdCl₄²⁻ and PdBr₄²⁻, and analogous bands for Hg²⁺ and Ag⁺ with 1. For 1 these new bands are considered to be either of the charge transfer type or transitions within the C=S moiety. These new bands for the complexes with 2 are assigned to LMCT transitions of the S → M type. These spectral features are used to obtain information about the solution structures of the complexes that are formed between these metal ions and both 1 and 2.     

3nion-independent conformational ordering in iota-carrageenan: Disorder-order equilibria and dynamics

The equilibria and dynamics of the disorder-to-order transition of the anionic polysaccharide iota-carrageenan have been studied in the presence of tetramethyl-ammonium salts. By the use of a stopped-flow polarimeter, the rate equation and temperature dependence of the observed forward rate-constant were found to accord with a co-operative dimerisation process. Activation parameters for helix nucleation were shown to be independent of the anion for solutions containing tetramethylammonium chloride and bromide, i.e., ΔH^‡ = 1 ±3 kJ.mol⁻¹, ΔS^‡ = −178 ±10 J.mol⁻¹.K⁻¹, ΔG^‡_298K = 54 ±2 kJ.mol⁻¹, and k_nuc,298K = 1880 ±80 dm³.mol⁻¹.s⁻¹. The temperature dependence of optical rotation was also shown to be independent of the anion present.