Kinetics of ligand exchange in uranyl complexes in non-aqueous solvents

Stopped flow and T-jump experiments were carried out to study the kinetics of the reactions leading to the formation of complexes of the forms UPL and UPL₂ where U stands for uranyl, P for TBP and L for 8-hydroxyquinoline or diphenylcarbazone. The experimental results, for CCl₄ and CH₂ClCH₂Cl solutions, provided considerable information on the mechanisms of these reactions as well as numerical values for some of the rate constants and activation energies and entropies.     

Polymer-induced synthesis of stable gold and silver nanoparticles and subsequent ligand exchange in water

A simple, inexpensive, single-step synthesis of gold and silver nanoparticles using poly(allylamine) (PAAm) as a reducing and stabilizing agent is reported. The synthetic process was carried out in aqueous solution, making the method versatile and environmentally friendly. The synthesized polymer-stabilized nanoparticles are stable in water without particle aggregation at room temperature for at least a month. We demonstrate successful ligand exchange on the polymer-stabilized gold nanoparticles (AuNPs) with a variety of omega-functionalized acid-, alcohol-, amine-, and biotin-terminated alkylthiols. The methodologies, including ligand exchange, also are applicable for the generation of finely dispersed silver nanoparticles. The synthesized gold and silver nanoparticles are characterized by UV-visible absorption spectroscopy and transmission electron microscopy (TEM). The different ligand-stabilized AuNPs are also analyzed by Fourier transform infrared (FTIR) spectroscopy.     

煤焦吸附和还原NO的动力学研究

利用固定床反应器研究了煤焦吸附和还原NO的动力学,分析了热解温度(500℃～900℃)和矿物质对煤焦脱除NO的影响。结果表明,在程序升温反应(TPR)和等温反应中,随着温度的升高(30℃～600℃),煤焦-NO经历了从化学吸附到还原反应的转变。低温时煤焦脱除NO的动力学符合Elovich方程,原煤焦的起始吸附速率随着温度的升高而增大,脱灰煤焦的起始吸附速率先增大后减小,等温吸附过程中煤焦的活化能随着吸附量的增大而增大。随着热解温度的升高,TPR中煤焦的NO转化率降低,等温还原反应的速率常数减小,高温热解导致煤焦脱除NO的活性降低。矿物质对煤焦-NO的吸附和还原反应存在催化作用。     

Kinetics of isoleucine chemisorption on the modified silica surface

Russian Journal of General Chemistry - Kinetics of isoleucine chemisorption on the modified silica surface involving an amide bond formation was studied. The grafted amino groups acting as...     

Crystal engineering of metalloporphyrin assemblies. New supramolecular architectures mediated by bipyridyl ligands

Targeted synthesis of new supramolecular motifs of metalloporphyrins in crystals by a concerted mechanism of molecular recognition in three dimensions, aided by organic ligands, is presented; it involves induced assembly of [tetrakis(4-hydroxyphenyl)porphyrinato]zinc species by a combination of axial coordination through bridging bipyridyls and of lateral hydrogen bonding.     

Syntheses, emission properties and intramolecular ligand exchange of zinc complexes with ligands belonging to the tmpa family

The zinc complexes [(L1)(2)Zn(MeOH)(2)](OTf)(2), [(L1)ZnCl(2)], [(L2)ZnCl(2)], [(L2)Zn(OTf)(H(2)O)]OTf and [(Me-bispic)ZnCl(2)] of the ligands N-[(2-pyridyl)methyl]-2,2'-dipyridylamine (L1), N-[bis(2-pyridyl)methyl]-2-pyridylamine (L2) and N-methyl-[bis(2-pyridyl)methyl]amine (Me-bispic) were synthesised and characterised. The first copper(I) complexes of the ligands L1 and L2 were also synthesised and structurally characterised. [(L1)ZnCl(2)] showed unexpected fluxional behaviour in solution and revealed an interesting intramolecular ligand exchange mechanism in the coordination sphere of the zinc ion. Furthermore, strong blue emission was observed under UV-light excitation.     

Kinetics of grafting acrylonitrile onto starch

Acrylonitrile (AN) was graft copolymerized onto gelatinized and granular wheat starch in aqueous media in the presence of ceric ammonium nitrate initiator at 91-364 anhydroglucose units (AGU) per cerium (IV) and at 1.08-4.33 AN to AGU ratios. Molecular weights and dispersities of polyacrylonitrile side chains were determined by gel-permeation chromatography. Conversion-time plots of AN polymerizations in both gelatinized and granular starch systems show characteristics common to heterogeneous polymerizations that could be explained on the basis of buried polymer radicals. The rates of polymerizations were directly related to the square root of the corrected cerium(IV) concentration and to the 1.3 power of the AN concentration. Graft copolymerization of AN onto starch, at least during initial stages, is not suitably explained by a kinetic scheme involving termination by polymer radical with cerium(IV) ion.     

Thiol-functionalized, 1.5-nm gold nanoparticles through ligand exchange reactions: scope and mechanism of ligand exchange

Ligand exchange reactions of 1.5-nm triphenylphosphine-stabilized nanoparticles with omega-functionalized thiols provides a versatile approach to functionalized, 1.5-nm gold nanoparticles from a single precursor. We describe the broad scope of this method and the first mechanistic investigation of thiol-for-phosphine ligand exchanges. The method is convenient and practical and tolerates a surprisingly wide variety of technologically important functional groups while producing very stable nanoparticles that essentially preserve the small core size and size dispersity of the precursor particle. The mechanistic studies reveal a novel three-stage mechanism that can be used to control the extent of ligand exchange. During the first stage of the exchange, AuCl(PPh3) is liberated, followed by replacement of the remaining phosphine ligands as PPh3 (assisted by gold complexes in solution). The final stage involves completion and reorganization of the thiol-based ligand shell.     

Kinetics of ligand exchange of aminoacid anions in the ternary complexes of copper(II) and hydroxyethyldenediphosphonic acid

The kinetics of the chemical exchange of some aminoacid anions in ternary complexes of copper(II) and hydroxyethylidenediphosphonic acid has been studied by a nuclear magnetic relaxation method. Rate constants of the chemical exchange have been determined and some suggestions concerning the structure of the complexes have been made.

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(II) . .

     

A trans-ortho asymmetrically di-strapped metalloporphyrin integrating three key structural features of ligand in heme

Heme responsible for the dioxygen fixation, transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand. In this work, a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of trans-precursor of porphyrinogen. Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere (SCS) bulks, maintaining a unique dome deformation, and making atomic out-of-plane deviation. In this way, this metallic complex integrates at least three key features of the pocket structure, the differentiated axial ligations, and the ring distortion, making it an ideal heme analog.     

Kinetics of addition of butyllithium onto diisopropenylbenzene

The kinetics of the addition reaction between butyllithium and diisopropenylbenzene (DIB) were investigated in non-polar solvents. It has been established that the two double bonds of meta-DIB are almost isoreactive, as expected; for the para-isomer however the first addition is faster than the second. The overall rate of reaction is also greater for para-DIB. This kinetic study is of great use, since the diadduct behaves as an efficient bifunctional anionic initiator which can be used in non-polar solvents.     

Separation of amines by ligand exchange: Part IV ligand exchange with chelating resins and cellulosic exchangers

Chelating, sulfonic and cellulosic exchangers were compared in ligand exchange chromatography. Chelating resins retain metal ions the best, but have a low ligand binding capacity. Cellulosic exchangers show excessive metal leakage. Sulfonated polystyrene resins loaded with nickel ions give best results in most cases. Data are presented on ligand exchange chromatography of simple aliphatic amines, hydrazine and substituted hydrazines, purine and pyrimidine bases.     

An unusual example ofendo-stereoselectivity in the ligand exchange reactions of rhodium(i)diethylene derivatives withpara-semiquinoid ligands

The ligand exchange reactions of [(C₂H₄)₂Rh(acac)] in benzene and [(C₂H₄)₂RhCl]₂ in CH₂Cl₂ with 4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one occur with 100%exo-stereoselectivity. The similar process with 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-4,6-dioxocyclohexylidene)-2,5-cyclohexadiene (trienedione) is strictlyexo-stereospecific only if [(C₂H₄)₂Rh(acac)] in benzene is used, while in the case of [(C₂H₄)₂RhCl]₂ in CH₂Cl₂, it proceeds with anendo-stereoselectivity of 43%. An explanation for these facts has been suggested that assumes that the metal atom initially attacks the central double bond in the trienedione, which is removed from the area of main steric hindrance. The subsequent metallotropic rearrangement of the resulting ethylene-triene intermediate gives rise to the final ⁴-coordinated -diene structures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2320–2323, September, 1996.     

Competitive chemisorption between pairs of cinchona alkaloids and related compounds from solution onto platinum surfaces

Quinoline-derived compounds exhibit the following relative chemisorption strengths from CCl4 solutions onto platinum surfaces, as determined by in-situ infrared spectroscopy: quinine, quinidine > cinchonidine > cinchonine > 6-methoxyquinoline > lepidine > quinoline. This sequence explains nonlinear enantioselectivity effects with cinchona chiral modifiers in hydrogenation catalysis.     

Kinetics and mechanism of the amine exchange reactions of 2-aminopyridine derived Schiff-base ligands and their copper(II) complexes

The kinetics and product analyses of the amine exchange reactions of two 2-aminopyridine derived Schiff-base ligands and their monomeric bischelate and dimeric copper(II) complexes have been studied. The Schiff-base ligands investigated underwent amine exchange reactions with n-butyl, cyclohexyl, t-butyl amines. The coordination of the Schiff-base ligands to copper(II) rendered the amine exchange reactions slower. With n-butyl and cyclohexyl amines, parallel first- and second-order terms on their concentrations are observed for the amine exchange reactions of copper(II) bischelates and dimer. The kinetic data favor a mechanism involving a rate-limiting elimination of 2-aminopyridine from a diaminoacetal intermediate in preference to a scheme in which a dissociation of the complexes into free ligands and Cu(II) may precede the amine exchange. The steric factors influence the amine exchange reactions of Cu(II) bischelates with the bulkier amines reacting slower as given by the order t-butylamine (3.3 ± 0.3 × 10^?3 dm³/mol·s) < cyclohexylamine (0.2 ± 0.03 dm³/mol·s) < n-butylamine (2.2 ± 0.2 dm³/mol·s). The bulkiness of the t-butyl group and the constraints imposed by the changes in the coordination geometry of Cu(II) on amine exchange not only render the reactions of Cu(II) bischelates slower but also make the formation of the mixed adduct ([N-(5-methyl)-2-pyridyl salicylaldimine][N-t-butyl salicylaldimine] Cu(II)) more favored.