铀酰配合物单晶的合成与结构

铀作为重要的核材料,是核燃料循环中最受关注的元素之一。在铀的开采、纯化以及应用等过程中,不可避免地会产生铀的释放。环境中的无机酸根及土壤有机质的羧酸根可与铀形成配合物,从而可能影响其迁移与吸附行为。通过研究铀酰配合物晶体的结构可以为吸附或迁移模型以及从分子水平探讨吸附机理提供结构参数。本文综述了国际上铀酰固体化学领域的研究进展,阐述了铀酰配合物的结构特点,铀酰无机含氧酸、过氧及草酸配合物的合成与晶体结构。在对国内外主要开展铀酰配合物晶体研究的课题组之研究工作进行归纳和分析的基础上,提出铀酰配合物研究的思路和建议,以期为国内锕系元素固体化学研究工作的开展提供参考。     

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U^VIO₂ ²⁺) coordinated by formate or acetate ligands. Anionic complexes containing U^VIO₂ ²⁺ and formate ligands fragment by decarboxylation and elimination of CH₂=O, ultimately to produce an oxo-hydride species [U^VIO₂(O)(H)]^-. Cationic species ultimately dissociate to make [U^VIO₂(OH)]⁺. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH₃CO₂?, with associated reduction of uranyl to U^VO₂ ⁺. Subsequent CID steps cause elimination of CO₂ and CH₄, ultimately to produce [U^VO₂(O)]^–. Loss of CH₄ occurs by an intra-complex H⁺ transfer process that leaves U^VO₂ ⁺ coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH₂=C=O to leave [U^VO₂(O)]^–. Elimination of CH₄ is also observed as a result of hydrolysis caused by ion-molecule reaction with H₂O. The reactions of other anionic species with gas-phase H₂O create hydroxyl products, presumably through the elimination of H₂.

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Structural Features of ONS-Donor Salicylidene Schiff Base Complexes

This review article summarizes the structural features of complexes of salicylidene Schiff bases containing, in addition to the phenolic-OH and the azomethine (–RC=N–) groups, a thiole group, and/or a sulfur atom participating in coordination. Structural aspects of metal complexes of salicylidene-2-aminothiophenol, salicylidene-3-aminothiophenol, salicylidenethiosemicarbazone, salicylidenedithiocarbazates, salicylidenedithiocarbazates, salicylideneaminopropyleneaminocyclopentenedithiocarboxylates, salicylideneimidazoles, and salicylidene-thiosalicylidene-1,3-propanediamine are reported.     

Uranyl Methacrylate Complexes with Carbamide and Methylcarbamide: Synthesis and Structure

The synthesis and X-ray diffraction and IR spectroscopic study of (UO₂)₂(mac)₄(L)₃ · H₂O crystals, where mac^– is the methacrylate ion C₃H₅COO^– and L is carbamide (I) or methylcarbamide (II), have been performed. Complexes I and II have a homotypic structure: crystals contain two kinds of mononuclear uranium-containing complexes, i.e., cationic [UO₂(mac)(L)₃]⁺ and anionic [UO₂(mac)₃]^–. The crystallographic formula of complexes in structures I and II is AB⁰¹M ₃ ¹ + AB ₃ ⁰¹ (A =UO₂²⁺ B⁰¹ = mac^–, M¹ = L). The uranium-containing complexes in structures I and II are linked into a framework by means of electrostatic interactions and a system of hydrogen bonds. Despite the similar compositions and structures of the uranium-containing complexes, their packings into a three-dimensional framework appreciably differ from each other.     

Modulation of the unpaired spin localization in Pentavalent Uranyl Complexes

The electronic structure of various complexes of pentavalent uranyl species, namely UO₂⁺, is described, using DFT methods, with the aim of understanding how the structure of the ligands may influence the localisation of the unpaired 5f electron of uranium (V) and, finally, the stability of such complexes towards oxidation. Six complexes have been inspected: [UO₂py₅]⁺ (1), [(UO₂py₅)KI₂] (2), [UO₂(salan-^tBu₂)(py)K] (3), [UO₂(salophen-^tBu₂)(thf)K] (4), [UO₂(salen-^tBu₂)(py)K] (5), [and UO₂-cyclo[6]pyrrole]^1? (6), chosen to explore various ligands. In the five first complexes, the UO₂⁺ species is well identified with the unpaired electron localized on the 5f uranium orbital. Additionally, for the salan, salen and salophen ligands, some covalent interactions have been observed, resulting from the presence of both donor and acceptor binding sites. In contrast, the last complex is best described by a UO₂²⁺ uranyl (VI) coordinated by the anionic radical cyclopyrrole, the highly delocalized π orbitals set stabilizing the radical behaviour of this ligand.     

Flexible Structural Features of Pentafulvene Titanium Derivatives: Isolation and Characterization of NHC Complexes

The reaction of η⁵,η¹‐pentafulvene titanium complexes with the strong N‐heterocyclic carbene (NHC) donor 1,3,4,5‐tetramethylimidazole‐2‐ylidene, leads to the formation of isolable NHC titanium adducts, featuring a haptotropic shift of the pentafulvene ligand, proved by single crystal X‐ray diffraction as well as NMR spectroscopy studies.     

Uranyl Sulfoxide Complexes as Photoinitiators of Polymerization of Methyl Methacrylate and Epoxy Acrylate Oligomers

Photoinitiation activity of uranyl sulfoxide complexes in polymerization of methyl methacrylate and epoxy acrylate derived from ED-16 and acrylic acid, and also the postirradiation effects in photopolymerization of these monomers were studied.     

Kinetics of Thermal Decomposition and Kinetics of Substitution Reaction of Nano Uranyl Schiff Base Complexes

This study focuses on the synthesis, characterization, and kinetics of substitution reaction of new uranyl Schiff base complexes prepared in a crystalline state as well as in a form of nanoparticles with sizes ranging between 35 and 60 nm. Preliminary Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) measurements indicated no difference between the two forms. The compounds were characterized by UV–vis, ¹H NMR, cyclic voltammetry, X‐ray crystallography, FTIR, TG, and CHN analyses. X‐ray crystallography revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven‐coordinated uranium. Cyclic voltammetry of the complexes in acetonitrile revealed the quasi‐reversible redox reaction. The TG and analysis of Coats–Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first order in all stages. The study of the kinetics and the mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was performed by the spectrophotometric method. The second‐order rate constants at four temperatures and the activation parameters revealed an associative mechanism for all corresponding complexes. Anticancer activity of the nano uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by the MTT (3‐[4,5‐dimethylthiazol‐2‐yl]‐2,5‐diphenyl‐tetrazoliumbromide) assay.     

水溶液中碳酸铀酰化合物的电子结构

应用相对论密度泛函理论系统研究了水溶液中非水合化和水合化碳酸铀酰化合物Cn/m(其中n和m分别为结构中碳酸配体和水配体的个数)的结构.溶剂效应采用类导体屏蔽模型(COSMO),并采用零级规整近似(ZORA)方法考虑标量相对论效应和旋-轨耦合相对论效应.电子跃迁采用包含旋-轨耦合相对论效应的含时密度泛函理论并在相关交换势中采用轨道势能统计平均(SAOP)做近似计算.结果表明碳酸配体对配合物结构和电子跃迁有很大的影响.C3/0配合物的稳定性可归于5f轨道参与了高占据轨道的成键作用.增加碳酸盐配体导致最大波长的蓝移,并在近可见光区域出现高强度的吸收.     

How the Substitution Faraway from NHCs Affects the Structural Features and Catalytic Activity of Dicarbene Dipalladium Complexes

A series of [PdPyCl₂]₂(di‐NHC) complexes were prepared (di‐NHC are two 1‐(2,6‐dimethylphenyl)imidazolidene molecules bridged by an aliphatic –(CH₂)_n– linker (n = 3, 4, 5, 6, and 10)). All complexes were fully characterized by NMR spectroscopy and elemental analyses. The crystal structures of four complexes (n = 3, 4, 5 and 6) were determined by X‐ray diffraction. The influence of the distant methyl group on the structural features and catalytic activity with increasing of length of linker was investigated by comparing the results of these 2,6‐dimethylphenyl palladium complexes with those of their known mesityl analogues. X‐ray studies show the distant methyl substitution has big impact on the structure feature of the complexes with the shorter linker between two NHC (ethylene and propylene), but has a little or no effect on that of the complexes with longer linker (butylene and hexylene). Catalytic results of the arylation of styrene show that the remote substitute has big effect on the regioselectivity of the product in all complexes with shorter and longer linkers, but has a limited effect on the yield.     

Synthesis and Structural Features of New Schiff Base Complexes of Mononuclear MnIV,Dinuclear CoIICoIII,and Tetranuclear CuII

2‐(((2‐Hydroxy‐3‐methoxyphenyl)methylene)amino)‐2(hydroxymethyl)‐1,3‐propanediol (LH₄, as abbreviation) reacts with MnCl₂ · 4H₂O, CoCl₂ · 6H₂O, and Cu(ClO₄)₂ · 6H₂O to give the new complexes [Mn(LH₂)₂] ( 1 ), [Co₂Cl(H₂O)(LH₂)₂] · 4H₂O ( 2 ), and [Cu₄(LH₂)₄(H₂O)₄] ( 3 ). Complex 1 is formed by the assembly of two molecules of the ligand with one manganese(IV) ion. In the mixed‐valence cobalt complex 2 there is an asymmetry between the coordination spheres of cobalt(II) and cobalt(III). In the tetramer 3 four copper(II) ions attain a distorted tetrahedral configuration surrounded by four molecules of the ligand.     

Kinetic Studies of Substitution Reactions of Uranyl(VI) Schiff Base Complexes with Tributylphosphine

The kinetics of the substitution reaction of uranyl Schiff base complexes with tributylphosphine was studied spectrophotometrically in acetonitrile. Uranyl complexes have a pentagonal bipyramidal structure with a trans‐UO₂ moiety at the axial positions. In uranyl tetradentate Schiff base complexes, the fifth position of the equatorial plane is occupied by the solvent molecule, which weakly coordinates to the U center. In a substitution reaction, tributylphosphine can easily replace the solvent molecule. By considering the excellent linearity of k_obs versus the molar concentration of tributylphosphine, the large negative values of Δ S^#, and the small values of Δ H^#, an associative (A) mechanism has been suggested. By comparing the rate constants (k₂) and the activation parameters, it is obvious that two parameters are effective in the rate of substitution reactions; The first parameter is the steric effect that the rate of reaction has been decreased by increasing this factor, and the other parameter is the electronic property that the electron‐withdrawing group leads to increase the rate of reaction and the electron donor group decreases it. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 168–174, 2013     

Structural Features of Silatranes and Germatranes

In stabilization of the endo configuration of silatranes and germatranes, a major role is played not only by the Si (or Ge) and N atoms, but also by oxygen and other atoms of the atrane core, which is manifested in molecular orbital parameters. Calculation of the system of interacting methyltrimethoxysilane and trimethylamine shows that the energy of the system grows as the distance between the Si and N atoms is decreased from 5 to 2 Å. The Si-N interaction in methylsilatrane, according to the calculations and precision X-ray diffraction studies, is the interaction of filled electronic shells and is electrostatic in nature. Analysis of the thermodynamic functions of formation of 1-methyl- and 1-hydroxysilatranes and -germatranes reveals an increase in the enthalpy and the decisive contribution of the entropy factors to stabilization of the reaction products. A ¹H NMR study of ethylgermatrane in aqueous solution revealed its equilibrium with the hydro- lyzed form. The transition state in the first step of hydrolysis of methyl- and hydroxysilatranes and -germatranes was studied by methods of quantum chemistry (AM1, PM3; basis sets STO-3G, 6-31G, 6-31G*, 6-31G** B3LYP method).     

Structural Diversity of F-Element Monophthalocyanine Complexes

The preparation and structural characterization of a series of lanthanide and uranium(IV) phthalocyanine halide complexes were achieved by reaction of the corresponding metal halide with Li₂Pc. A preliminary survey of their reactivity includes ring reduction of Li(THF)₄[PcUCl₃] with KC₈ leading to the first structurally characterized Pc⁴⁻ actinide complex, hydrolysis of PcDyCl(DMSO) to PcDyOH(H₂O)₃ and preparation of a unique trimeric triangular Li(PcDy)₃(OH)₄(H₂O) cluster.