配体化合物对催化剂性能的影响

以氧化铝为载体,采用饱和浸渍法制备含有不同配体化合物的加氢催化剂,采用程序升温还原方法(TPR),X射线光电能谱(XPS)、高分辨率透射电镜(HRTEM)等分析手段考察配体化合物对催化剂性能的影响。结果表明:催化剂中添加配体化合物,能够削弱活性组分与载体间的相互作用力,增加活性前驱体八面体钼聚合物含量;改善活性组分在载体表面的分散度;增加高活性Ni-Mo-SⅡ类活性位的数目。评价结果表明,添加配体化合物能够显著提高催化剂活性组分的有效利用率,与不含助剂的催化剂相比,当催化剂中含有赖氨酸时其相对脱硫活性为118%,相对脱氮活性为123%。

N,O-二齿配体化合物的设计合成

以2,6-二甲基吡啶、正丁基锂为初始原料,在温和的条件经一倍正丁基锂去氢后与环己酮加成得到含N,O-二齿配体化合物[2-(6-(CH3)C5H4N)CH2C(OH)(CH2)4CH2],应用1H NMR技术对其进行了结构表征。

一种钯配体化合物的合成

以2-萘胺为原料在氯化铜的作用下经过氧化偶联重排,得到1,1′-联萘-2,2′-二胺,然后依次经过重氮化、溴代和甲基化,得到2′-溴-2-N,N-二甲基-1,1′-联萘胺,收率49.7%。该联萘化合物在正丁基锂作用下,与二叔丁基氯化膦反应,得到最终的目标化合物,收率66.9%。4步反应的总收率33.3%。

原位构筑配体偶联P(V)平台合成α-氨基酸酯类化合物

本文主要利用三价膦与邻二羰基化合物的Kukhtin-Ramirez反应中间体原位构筑五配体磷类化合物作为配体偶联的反应平台,一步法实现了α-氨基酸酯类化合物的高效合成。该方法创新性地利用了Kukhtin-Ramirez中间体原位转化为五配体磷类化合物,为需要预合成五配体磷类化合物的传统配体偶联反应模式提供了新的探索方向。In this work, the Kukhtin-Ramirez reaction intermediates from trivalent phosphine and α-dicarbonyl compounds were used to in situ construct pentacoordinated phosphorus compounds as the reaction platform of ligand coupling for the synthesis of α-amino carboxylic esters which was realized in one-step. This approach innovates in the in-situ conversion of Kukhtin-Ramirez inter-mediates into pentacoordinated phosphorus compounds, providing a new direction for the traditional ligand coupling reaction mode that requires pre-synthesis of pentacoordinated phosphorus compounds.

ICP-OES测定双齿膦配体钯类化合物的含量

180℃条件下,于聚四氟乙烯消解罐加压消解双齿膦配体钯类化合物样品,研究了电感耦合等离子体发射光谱法(ICP-OES)测定双齿膦配体钯类化合物中钯含量的方法。采用ICP-OES法测定四种双齿膦配体钯类化合物样品,钯的检测值和理论值相近,结果准确,该检测法简便、快速,表明该检测法适合双齿膦配体钯类化合物中钯含量的测定。

ThermalShift高通量筛选法快速筛选覆盆子中雌激素样活性化合物

[目的]从覆盆子中筛选具有雌激素样活性的化合物。[方法]基于配体=受体理论,以人源雌激素受体亚型的配体结合域(hERα-LBD、hERβ-LBD)为靶点,以17β-雌二醇(E_2)为阳性对照,采用Thermal Shift高通量筛选方法筛选覆盆子中具有雌激素样活性的化合物。[结果]山柰酚明显提高雌激素受体配体结合域的(hERα-LBD、hERβ-LBD)热稳定性。[结论]山柰酚能与hERα-LBD和h ERβ-LBD结合,具有雌激素样活性。

N,O-配体钴化合物的合成及其环氧丙烷羰化酯化的催化性能

合成了9种N,O-配体化合物L^(1)~L^(9).化合物L^(1)~L^(4)分别与0.5 equiv.Co_(2)(CO)_(8)发生氧化还原配位反应生成中性单核钴化合物1~4;L^(5)~L^(7)分别与1 equiv.Co_(2)(CO)_(8)发生歧化和氧化还原配位反应;L8与5/6 equiv.Co_(2)(CO)_(8)以及1.2equiv.MeOH和0.4 equiv.H_(2)O发生歧化和氧化还原配位反应;L^(9)与0.5 equiv.Co_(2)(CO)_(8)发生歧化配位反应生成同钴核离子对化合物5~9.这些化合物中的阴离子均为[Co(CO)4]-.相应地,化合物8中的阳离子是三核钴簇,其它化合物中的阳离子都是单核钴.化合物1~9通过FT-IR谱学表征和元素分析数据确定,其中1和8进一步经过X射线单晶结构确认.考察了化合物1~9催化环氧丙烷(PO)羰化酯化的性能,获得42.6%~99.0%的PO转化率和34.1%~88.6%的β-羟基丁酸甲酯(HMB)总产率.研究了8和9随时间变化的催化反应,推测了同钴核离子对协同作用的催化反应机理.

Syntheses,crystal structures,and quantum chemistry calculation of two Ni(Ⅱ)coordination polymers

Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.

含CS配体的单、双核钌羰基化合物Ru(CS)(CO)_n(n=4,3)和Ru_2(CS)_2(CO)_n(n=7,6,5,4)的理论研究

采用2种密度泛函方法MPW1PW91和BP86对中性单核Ru(CS)(CO)n(n=4,3)及双核Ru2(CS)2(CO)n(n=7,6,5,4)化合物进行理论计算研究,优化出25个异构体.研究发现,单核配位饱和Ru(CS)(CO)4的2个异构体14-1,14-2能量接近,其配体呈三角双锥型.对称性为C2v的异构体14-1能量稍低,其CS基团在三角双锥赤道面上.单核配位不饱和Ru(CS)(CO)3的能量最低异构体是由14-1失去1个赤道面上的CO得到的,其对称性为Cs.配位饱和的双核Ru2(CS)2(CO)7能量最低异构体27-1结构中有3个桥配位基团,其中2个是CS基团.配位不饱和的Ru2(CS)2(CO)6存在2个能量接近的异构体,即含3个桥配位基团对称性为Cs的异构体26-1和含2个桥配位基团的异构体26-2.它们的CS基团都是桥配位形式.Ru2(CS)2(CO)5的能量最低异构体25-1含有两个桥配位CS基团,其中一个是4电子供体.而Ru2(CS)2(CO)4的能量最低异构体24-1的两个桥配位CS基团都是4电子供体.在上述各个异构体中,单核Ru(CS)(CO)n(n=4,3)的能量最低异构体的CS基团都位于配体三角双锥及缺顶点结构的赤道面上,双核Ru2(CS)2(CO)n(n=7,6,5,4)能量最低异构体的CS基团都以桥配位形式和Ru原子相连,且在配位不饱和Ru2(CS)2(CO)n(n=5,4)的能量最低异构体中都存在4电子供体CS基团.离解能研究表明,单核配位饱和的Ru(CS)(CO)4具有一定的热力学稳定性.双核的Ru2(CS)2(CO)n(n=7,6,5)失去1个CO或者分裂为单核的Ru(CS)(CO)4或Ru(CS)(CO)3所需能量都较高,但Ru2(CS)2(CO)6和Ru2(CS)2(CO)5有发生歧化反应的趋势,而Ru2(CS)2(CO)7具有一定的热力学稳定性.

新型膦胺配体羰基钌化合物的合成及其催化性能研究

以十二羰基三钌和o-PPh2C6H4NR2(R=H,Me)配体为原料,成功制备了三种新型羰基钌化合物(μ-o-PPh2-C6H4NH)Ru3(μ-H)(CO)9(2)、(o-PPh2C6H4NH)2Ru(CO)2(3)和(μ-o-PPh2C6H4NMe2)2Ru(CO)3(4).对这三个化合物进行了核磁共振和红外谱学、元素分析和X射线单晶衍射分析表征,并对这三个化合物进行了催化性能研究.化合物2和4可催化苯甲醛加氢反应生成苯甲醇,但是3没有催化活性.从实验角度阐述了膦胺配体钌催化剂的结构与性能关联,进一步探讨了加氢催化反应失活的可能原因.

Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction

The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.

Synthesis and Structure of Copper(Ⅱ) Complex [Cu(C_5H_5N)_2(H_2O)(C_6H_5COO)_2]

At room temperature, the reaction of dibenzoyl peroxide with metallic copper powder in the presence of pyridine affords the copper(Ⅱ) complex [Cu(C 5H 5N) 2(H 2O)\|(C 6H 5COO) 2]. Crystal is monoclinic, M r =483.002, space group Cc with parameters: a=6\^078(4), b=15.879(4), c=23.091(3), β=97.61(2)°, V=2209.1(2) 3, Z=4, D c =1\^464g/cm 3, μ =10.279 cm -1 , F(000)=996, R=0\^031, R w =0.036, 1595 reflections with I≥3σ(I ) were considered to be observed. Each copper(Ⅱ) ion is coordinated by two monodentate benzoate ligands, two pyridines and one water molecule. The complex is also characterized by its IR, XPS and thermal properties.

Synthesis,Structural Characterization and Magnetic Properties of{[Gd(DMF)_(3)(DMSO)(H_(2)O)_(3)](μ-CN)(Fe)(CN)_(5)]}·2H_(2)O

A new cyano-bridged Gadolinium^(Ⅲ)-Iron^(Ⅲ)complex{[Gd(DMF)_(3)(DMSO)(H_(2)O)_(3)]2H_(2)0(DMF=N,N·-dimethylformamide;DMSO=dimethylsulfoxidel}was synthesized by the grinding reaction method,.It crysta-]llizes in the triclinic.,space group P1 with ceIl parameters:a=O.90363(2)nm,b=1.25078(3)nm,c=1.41303(1)nm,穋m^(-3),Z=2,Mr=756.72,F(000)=760,Ⅲ)and the approxi-mately oriented octahedrally sixfold-coordinated Fe(Ⅲ)are linked by a cyano-bridge group to construct a dinuclear compound.The{[Gd(DMF)_(3)(DMSO)(H_(2)O)_(3)](Ⅲ)-Fe(Ⅲ)interaction is antiferromagnetic.CCDC:223430.

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer: [(C_(22)H_(50)N_2)(Ag_2I_4)]_n

A novel coordinated polymer [(C22H50N2)(Ag2I4)]n([C22H50N2]2+ = N,N?-1,2- ethylence-bis(N,N?-dimethyl octane ammonium) (EDO)) was synthesized by the reaction of AgI and EDO at room temperature with pH = 6.8, and structurally characterized by means of X-ray single- crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.6080(1), b = 12.7643(2), c = 7.2157(8) ? a = 100.835(8), ?= 91.030(3), ? = 91.297(9)o, (C21.50H48.50Ag2I4N2), Mr = 1058.46, V = 868.71(19) 3, Z = 1, Dc = 2.023g/cm3, F(000) = 497.5, ?MoKa) = 4.692 mm-1, the final R = 0.0623 and wR = 0.1949 for 2641 observed reflections with I > 2s(I). The title compound consists of cations ([C22H50N2]2+) and anion chain (Ag2I42-)∞ which are combined by static attracting forces in the crystal to form the so-called organic-inorganic hybrid material.

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.

Synthesis of polymer/CNTs composites for the heterogeneous asymmetric hydrogenation of quinolines

The development of heterogeneous catalytic processes is crucial for the synthesis of chiral compounds for both academic and industrial applications.However,thus far,such achievements have remained elusive.Herein,we report the heterogeneous asymmetric hydrogenation of 2-methylquinoline over solid chiral catalysts,which were prepared by the one-pot polymerization of(1R,2R)-N-(4-vinyl-benzenesulfonyl)-1,2-diphenylethane-1,2-diamine(VDPEN)and divinylbenzene(DVB)in the presence or absence of activated carbon(C)or carbon nanotubes(CNTs),followed by Ru coordination and anion exchange.The solid chiral catalysts were fully characterized by N2 sorption analysis,elemental analysis,TEM,FT-IR spectroscopy,and 13C CP-MAS NMR.All the solid chiral catalysts could efficiently catalyze the asymmetric hydrogenation of 2-methylquinoline to afford 2-methyl-1,2,3,4-tetrahydroquinoline with 90%ee.Studies have shown that polymer/C and polymer/CNTs composites are more active than pure polymers.The polymer/CNTs composite exhibited the highest activity among all the solid chiral catalysts under identical conditions,owing to the unique morphology of CNTs.The recycling stabilities of the solid chiral catalysts were greatly improved when ionic liquids(ILs)were employed as solvents;this is mainly attributed to the decreased leaching amount of anions owing to the confinement effect of ILs on ionic compounds.

Electrocatalytic hydrogen evolution from water at low overpotentials with cobalt complexes supported by redox-active bipyridyl-NHC donors

Three cobalt complexes bearing tunable,redox-active bipyridyl N-heterocyclic carbene(NHC)-based ligands have been studied for electrocatalytic hydrogen evolution from aqueous solutions.The effect of structural modifications to the ligand framework is investigated across the catalyst series,which includes a non-macrocyclic derivative(1-Co)and 16-(2-Co)and 15-(3-Co)membered macrocycles.A structure-activity relationship is demonstrated,in which the macrocyclic complexes have greater activity compared to their non-macrocyclic counterpart with the most rigid catalyst,supported by the 15-membered macrocycle,performing best overall.Indeed,3-Co catalyzes H2 evolution from aqueous pH 4 acetate buffer with a Faradaic efficiency of 97%at a low overpotential of 330 mV.Mechanistic studies are consistent with formation of a cobalt-hydride species that is subsequently protonated to evolve H2 via a heterolytic pathway.

Hydrothermal Synthesis and Crystal Structure of [(CH_3CH_2)_4N]_4[(La_(12)(OH)_(12)MoO_(29) )], A Novel Cluster Compound with a MoO_5 Hexahedron Center Surrounded by La-O Octahedron

A novel compound [(CH 3CH 2) 4N] 4[(La 12 (OH) 12 MoO 29 )] was synthesized by hydrothermal reaction. The single crystal X ray diffraction shows that the compound crystallized in the monoclinic space group C2/c ; a =2 5729(4) nm, b =1 4318(1) nm, c =2 1217(4) nm, β =111 56(1)°, V =6 8235(7) nm 3, Z =4, R =0 0751. The basic building blocks of the crystal structure included one MoO 5 hexahedron and twelve LaO 6 octahedra which shared a common edge to form a [(La 12 (OH) 12 MoO 29 )] 4- unit. These units were held together by the [(CH 3CH 2) 4N] + ions.

Synthesis and Crystal Structure of a New Imidazole Coordinated Octamolybdate Compound

The title compound (Himi)4[Mo8O26(imi)2]4H2O (imi = imidazole) 1 was synthe- sized by the reaction of H2MoO4 and imidazole in aqueous solution. Single-crystal X-ray analysis reveals that compound 1 is crystallized in the triclinic system, space group P with a = 10.6219(8), b = 10.7260(8), c = 11.3220(9) , a = 92.842(2), b =117.364(1), g = 101.655(1), C18H36Mo8N12- O30, Mr = 1668.11, V = 1106.8(2) 3, Z = 1, Dc = 2.503 g/cm3, F(000) = 804, m = 2.298 mm-1, the final R = 0.0714 and wR = 0.1651 for 3121 observed reflections with I > 2s(I). The X-ray crystal structure analysis suggests that compound 1 is built up by two imidazole ligands coordinated by the centrosymmetric octamolybdate anions, protonated imidazole cations and crystallization water molecules.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.