水杨醛缩乙醇胺双氧钒席夫碱配合物的合成、晶体结构及热分解研究(英文)

A new complex bis[(N-salicylidene-N’-ami noethanol)abstract:dioxovandium (Ⅴ)abstract:,[V (Ⅴ)abstract:(Ⅴ)abstract:(SALAE)abstract:]2 ,was synthesized by the reaction of salicylaldehyde and aminoethanol with va nadyl sulfate.It was characterized by elemental analysis,IR and X-ray single cr ystal diffraction analysis.The crystal of the title complex(C 18 H 20 N 2 O 8 V 2 ,M r =494.24)abstract:be-longs to monoclinic,space group P2 1 /c with the following crystallographic parameters:a=1.7966(6)abstract:nm,b=0.7587(3)abstract:n m,c=2.1539(7)abstract:nm,β =92.551(6)abstract:°,V=2.9329(17)abstract:nm 3 ,Z=6,D c =1.679g · cm -3 ,μ (MoK α )abstract:=1.006mm -1 ,F(000)abstract:=1512,and final R 1 =0.0563,wR 2 =0.1243for observed reflections2861(I>2 σ (I)abstract:)abstract:.The complex is a bis( μ -oxo)abstract:-bridged V schiff base dimer formed by two dioxovandium units,V is six-coordinated and forms a distorted octahedral structure.The thermal d ecomposition for the complex was studied by TG-DTG curves and the apparent acti vation energy was obtained by the Kissinger formula.CCDC:211147.

一个新的双氧桥联双核锰配合物[Mn~Ⅳ(naphtmen)(μ-O)]_2的合成、晶体结构和磁学研究

通过MnⅢnaphtmen H2O2ClO4(H2naphtmen=N,N'-二(2-羟基-1-萘甲醛)缩(1,1,2,2-四甲基乙二胺))和Li(TCNQ)(TCNQ=7,7,8,8-四氰基对苯二醌二甲烷自由基阴离子)反应,合成了一个中心对称的双氧桥联双核锰配合物MnⅣnaphtmen-O2(1).单晶X-射线衍射结果表明,配合物1属单斜晶系,2(1)/c空间群,a=13.277(3),b=10.066(2),c=16.960(3),β=97.28(3)°,V=2 248.2(8)3,Z=4,F(000)=760,μ=0.622 mm1,1=0.0438,w R2=0.112 2.中心Mn(Ⅳ)离子采取变形八面体的配位构型,分子内MnMn距离为2.7591,桥联键角Mn-O-Mn为99.36°.变温磁化率研究表明,配合物1双核单元内Mn(Ⅳ)离子间存在着弱的反铁磁相互作用:J=0.19 cm1,g=2.02.

反式双氧锰(V)咔咯配合物的稳定性

采用密度泛函理论(DFT)的B3LYP方法对反式双氧锰(V)咔咯配合物阴离子的稳定性及其质子化物种进行了理论计算.结果表明:反式双氧锰(V)咔咯配合物阴离子构型稳定,其反式双氧锰键O=Mn=O由锰原子的d轨道与两个氧原子的p轨道分别构成一个σ轨道和两个π轨道;随着外围取代基吸电性增强,O=Mn=O键长缩短,拉曼伸缩振动频率增大;其质子化过程中得到两个质子的轴向氧原子与锰原子的距离超出正常化学键的范围,从而形成水分子并脱离原来分子,导致质子化行为是不可逆过程,而形成单氧的咔咯锰(V)-氧配合物.

Synthesis and Crystal Structure of Bis(nitrate)- bis(N,N'-dimethyl-N,N'-dibenzenyl-urea)uranyl(Ⅱ)

The new uranyl complex UO2(NO3)2[PhN(CH3)C(O)(CH3)NPh]2 was synthesized and its crystal structure has been determined by single-crystal X-ray diffraction. Crystal data: C30H32N6O10U, triclinic, space group P with a = 7.772(1), b = 9.267(1), c = 12.644(1) ? a = 68.246(8), b = 73.871(9), g = 84.99(1)o, V = 812.4(2) ?, Mr = 874.65, Z = 1, Dc = 1.788 g/cm3, F(000) = 426, m = 5.062 mm-1, the final R = 0.022 and wR = 0.059 for 3571 observed reflections (I > 2s(I)). The central uranyl ion is coordinated by six oxygen atoms, two from the carbonyl groups of N,N-dimethyl-N,N-dibenzenyl-urea molecules and the other four from two nitrate groups.

Formation and Characterization of ZrO3 and HfO3 Molecules in Solid Argon

ZrO3 and HfO3 molecules were prepared via reactions of metal monoxides with dioxygen in solid argon and were characterized using matrix isolation infrared absorption spectroscopy as well as theoretical calculations. Unlike the titanium monoxide molecule, which reacted spontaneously with dioxygen to form TiO3, the ZrO and HfO molecules reacted with dioxygen to give the ZrO3 and HfO3 molecules only under visible light irradiation. Density functional calculations predicted that both the ZrO3 and HfO3 molecules possess a closed-shell singlet ground state with a non-planar C8 geometry, in which the side-on coordinated O2 falls into the peroxide category.

Preparations of Complex Bimetallic Oxides from Bimetallic Assemblies Containing Different Copper（Ⅱ） Precursors and Comparison of Some Related Systems

This is a mini-review-like article including our recent results and methods for （new） metal oxides and （previously reported） composite materials composed of metal complexes and metal oxides for comparison to enhance anisotropic structural changes intentionally. Some complex inorganic oxides are known that they may be promising color materials （absorbing visible light of certain wavelengths region） having potential application for environmentally benign catalysts, for example, photocatalysts. Chiral copper（Ⅱ） complexes having bidentate amine ligands （[CuL2]2＋） can be acted as cationic building blocks of bimetallic metal complexes. We have prepared some chiral bimetallic complexes with various anionic metal complexes such as [PtCl4]2-, [M02O7]2 and Mn12 clusters （typical single-molecule magnets） which characterized by means of solid-state electronic and CD （circular dichroism） spectra, IR （infrared） spectra, synchrotron XRD （X-ray diffraction） and XAS （soft X-ray absorption spectroscopy）. By sintering these precursor chiral bimetallic complexes, we have prepared complex inorganic oxides from them. The IR spectra indicated substituting metal-ligand bonds and losing organic moieties. The XRD pattern indicated complete changes of crystal structures. The XAS revealed replacing coordination atoms as well as oxidation of valences of metal ions. Furthermore, we will also investigate possibility of patterning by homogeneous precipitation method as bimetallic complexes to prepare desirable complex inorganic oxides.

Selective photocatalytic reduction of CO2 to CO mediated by a[FeFe]-hydrogenase model with a 1,2-phenylene S-to-S bridge

Photocatalytic reduction of CO2 to CO is a promising approach for storing solar energy in chemicals and mitigating the greenhouse effect of CO2.Our recent studies revealed that[(μ-bdt)Fe2(CO)6](1,bdt=benzene-1,2-dithiolato),a[FeFe]-hydrogenase model with a rigid and conjugate S-to-S bridge,was catalytically active for the selective photochemical reduction of CO2 to CO,while its analogous complex[(μ-edt)Fe2(CO)6](2,edt=ethane-1,2-dithiolato)was inactive.In this study,it was found that the turnover number of 1 for CO evolution reached 710 for the 1/[Ru(bpy)3]2+/BIH(BIH=1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]-imidazole)system under optimal conditions over 4.5 h of visible-light irradiation,with a turnover frequency of 7.12 min−1 in the first hour,a high selectivity of 97%for CO,and an internal quantum yield of 2.8%.Interestingly,the catalytic selectivity of 1 can be adjusted and even completely switched in a facile manner between the photochemical reductions of CO2 to CO and of protons to H2 simply by adding different amounts of triethanolamine to the catalytic system.The electron transfer in the photocatalytic system was studied by steady-state fluorescence and transient absorption spectroscopy,and a plausible mechanism for the photocatalytic reaction was proposed.

Anisotropic Thermally-Accessible Lattice Distortion of a Cu（ll）-Cr（VI） Complex Bimetallic Oxide by Adsorbing a Chiral One-Dimensional Cu（ll）-Cr（VI） Coordination Polymer

The authors have prepared and characterized a chiral one-dimensional Cu（II）-Cr（VI） coordination polymer, [CuL2][Cr207] （L = （IR, 2R）-diaminocyclohexane）, which exhibited intense d-d bands as well as charge transfer bands in the solid state electronic and CD spectra. Thermally-accessible lattice distortion was observed along the crystallographic a axis, which corresponded to Jahn-Teller distortion of Cu（II） chromophores. After firing [CuL2][Cr207], they could obtain a Cu（II）-Cr（VI） complex bimetallic oxide showing ferromagnetism and isotropic thermally-accessible lattice distortion. Preparation of composite materials of the coordination polymers and a complex bimetallic oxide could be confirmed by IR spectra and magnetic properties. It should be noted that the complex bimetallic oxide as the composite exhibited anisotropic thermally-accessible lattice distortion by adsorption of the chiral one-dimensional coordination polymer.

Synthesis and Crystal Structure of Potassium Triethylenetetraaminehexaacetatodi [Oxo-vanadium(Ⅳ)] Hexahydrate, K_2[V_2O_2(ttha)]·6(H_2O)

The title complex, potassium triethylenetetraaminehexaacetatodi [oxo-vanadium (Ⅳ)] hexahydrate K2[V2O2(ttha)]6(H2O), was synthesized in aqueous solution and its crystal structure has been determined by X-ray diffraction. The complex belongs to a triclinic system, space group P?with a = 6.645(1), b = 9.870(2), c = 13.263(3) ? a = 70.68(3), b = 76.27(3), g = 71.66(3), V = 770.5(3) 3, Mr = 808.58, Dc = 1.743 g/cm3, Z = 1, m = 0.968 mm-1, l(MoKa) = 0.71073 and F(000) = 416. The final R = 0.0465 and wR = 0.1091 for 2974 observed diffractions with I ≥ 2s(I). In the complex, the V atom is octahedrally coordinated to the oxo ligand, two N and three O atoms of the triethylenetetraaminehexaacetic (TTHA) ligand. All of the ten chelating sites are coordinated to the two vanadium atoms, and the coordination octahedron is distorted. Each [V2O2(ttha)]2- ion is further connected by the K+ ions through carboxyl groups of TTHA6- ion, forming a two dimensional network structure.

Oxygenolysis reaction mechanism of copper-dependent quercetin 2,3-dioxygenase:A density functional theory study

The mechanism of the action of copper-dependent quercetin 2,3-dioxygenase （2,3QD） has been investigated by means of hy- brid density functional theory. The 2,3QD enzyme cleaves the O-heterocycle of a quercetin by incorporation of both oxygen atoms into the substrate and releases carbon monoxide. The calculations show that dioxygen attack on the copper complex is energetically favorable. The adduct has a possible near-degeneracy of states between [Cu2＋-（substrate H＋）] and [Cu＋-（sub- strate-H）. ], and in addition the pyramidalized C2 atom is ideally suited for forming a dioxygembridged structure. In the next step, the C3-C4 bond is cleaved and intermediate lnt5 is formed via transition state TS4. Finally, the Oa-Ob and C2-C3 bonds are cleaved, and CO is released in one concerted transition state （TS5） with the barrier of 63.25 and 61.91 k J/tool in the gas phase and protein environments, respectively. On the basis of our proposed reaction mechanism, this is the rate-limiting step of the whole catalytic cycle and is strongly driven by a relatively large exothermicity of 100.86 kJ/mol. Our work provides some valuable fundamental insights into the behavior of this enzyme.