The Synthesis of Glycosyl Phosphite-Pt(II) Complexes

Sugar derivatives whose molecules contain trivalent phosphorus groups have been coming into use for different scientific purposes, including the synthesis of metal com- plexes. These metal complexes of glycosyl phosphites are effective chiral catalysts in enantioselective synthesis1-5such as hydrogenation, cyclopropylation, hydro phosphina- tion and hydrosilylation of achiral olefin. Furthermore, this kind of compounds are also widely applied in biology and medicine area and open up a new fie…     

Synthesis and Liquid Crystal Properties of Transition Metal Complexes of Mesotetra （4-n-myristyloxyphenyl） porphyrin

Transition metal complexes of meso-tetra (4-myristyloxyphenyl)porphyrin TMPPM′ [M′=Mn, Fe, Co, Ni, Cu, Zn ; TMPP=mesotetra (4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, ^1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7. 453℃ and a wide mesophase temperature span, 77℃.     

The Purification of Glucose Type Glycosyl Nitrate and the Synthesis of Spacer—armed N—Acetyllactosamines and Their Dimers

Our previous paper1,2reported the results of selective synthesis of mannose type glycosides and their dimers in our attempt to synthesize derivatives of N-acetyllacto- samine, which could have potential activity of anti-metastasis3. Further studies on the glycosylation of the accepters exploiting glycosyl nitrate instead of the acetate as donor showed interesting chemoselectivity between the two kinds of donor, namely, the glucose type and the mannose type. The reactivity difference of the t…     

Synthesis and Crystal Structure of cis—[meso—1,3—Bis（propylsulfinyl）propane]dichloroplatinum（Ⅱ）

1 INTRODUCTION A number of Pt complexes with monosulfoxide have been isolated and characterized[1]. It was indicated that the sulfoxide group trends to coordinate to soft metals (Pt, Pd, etc.) by its sulfur atom[2]. Pt(Ⅱ) trends to bond to disulfoxides in cis-mode and such complexes have potential antitumor activity[2]. However, only few examples of such complexes have been structurally characterized[3]. We will report herein the crystal structure of a new Pt(Ⅱ) complex with a disulf…     

Bis（ortho—）chelated Monoanionic Bisphosphinoaryl Ruthenium（Ⅱ）Complexes：Synthesis,Characterization and Reactivity

Bisphosphinoaryl ruthenium(Ⅱ）compounds are synthesized using two distinct synthetic routes.One route,direct cycloruthenation,consists of the reaction of the parent arene compound R-PCHP with [RuCl2(PPh3)3]in chlorinated solvents.However,this route suffers from major drawbacks because HCl is formed as well as free triphenylphoshine.The other route,the transcyclometalation reaction,involves the interconversion of one cyclometalated ligand metal complex,[RuCl(NCN)(PPh3)],into another complex,[RuCl(R-PCP)(PPh3)],with concomitant consumption and formation of the corresponding arenes R-PCHP and NCHN,respectively.     

Synthesis of N—（4—Salicylideneiminoaryl）monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt（Ⅱ）Complexes

The Schiff base‐containing pendant monoaza crown ether HL¹, HL², HL³ and HL⁴ have been synthesized by condensation of salicylaldehyde with N‐(4‐aminoaryl) monoaza crown ethers, which were prepared conveniently from 4‐nitro‐N, N‐di(hydroxyethyl) aniline or 4‐nitrobenzyl chloride via cyclization or condensation and reduction. The structures of HL¹—HL⁴ were verified by ¹H NMR, IR spectra, MS and elemental analysis. Moreover, the oxygenation constants (KO2) and thermodynamic parameters (δH⁰ and δS⁰) of their cobalt(II) complexes were determined in the range of ?5 °C to 25 °C, and the effect of crown ring bonded to a Schiff base on the dioxygen affinities of cobalt(II) complexes was also observed as compared to the uncrowned analogue (CoL).     

Synthesis and Magnetic Properties of Fe（Ⅱ） and Nd（Ⅲ） Complexes of Poly（N-2-thiazolylacrylamide）

N-2-Thiazolylacrylamide （NTA） was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy （EDX） were applied to characterize these materials. The magnetic behavior of Fe（Ⅱ） and Nd（Ⅲ） complexes of poly（N-2-thiazolylacrylamide） was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd（Ⅲ） complex has an extremely high relative saturation magnetization of 35 emu/g.     

Hydrothermal Synthesis and Crystal Structure of a Manganese（Ⅱ） Complex：Mn_（1.5）（cbba）_3（phen）

A new metal-organic complex Mn1.5(cbba)3(phen)(Hcbba = 2-(4'-chlorine-ben-zoyl)benzoic acid,phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectro-scopy.The compound crystallizes in triclinic,space group P1 with a = 12.137(2),b = 14.535(3),c = 14.894(3),α = 86.380(3),β = 70.381(3),γ = 72.647(3)°,V = 2360.3(8)3,C107H64Cl6Mn3N4O18,Mr = 2071.14,Dc = 1.457 g/cm3,μ(MoKα) = 0.638 mm-1,F(000) = 1055,Z = 1,the final R = 0.0638 and wR = 0.1905 for 6155 observed reflections(I > 2σ(I)).It exhibits a 3D supramolecular network through hydrogen bonding and π-π stacking interactions.     

Synthesis and Crystal Structures of the α and β Forms of Bis （salicylaldoxime） copper （ Ⅱ ） Complexes

IntroductionSalicylaldoxime can be used in chemically modi-fied glassy-carbon electrodes,and applied to the deter-mination of metals in water.It shows a very high recov-ery[1,2].Direct design of solid-state structures that en-compass frameworks such as grids,ladders,helicesand channels of a desired architecture is central to crys-tal engineering science[3,4].Each of the oxidationstates of copper displays a different stereochemistry,ofwhich Cu(Ⅱ)is the most representative example foritsd9elec…     

Synthesis,Structure and Magnitic Properties of a Diphenoxobridged Binuclear Copper（Ⅲ） Complex

A mixed-ligand copper(Ⅱ） complex[Cu2(phen)2(HL^1)2]-(ClO4)2(1) was synthesized.X-ray analyses reveal that 1 has a bis(μ2-phenoxo)-bridged dicopper(Ⅱ） structure.2D hydrogen-bonded network is formed utilizing the N-H,O-H and C-H groups of the (HL^1) ligands (H2L^1=N-(2-hydroxybenzyl)ethanolamine),the C-H groups of the phenanthrolines and the perchlorate anions.Variable temperature magnetic properties of 1 have shown comparatively weak antiferromagnetic interactions with respect to the bridge angles, which have been ascribed to the unfavorable overlaps of the magnetic orbitals fo the highly distorted copper coordination polyhedra and the pyramidal distortions at the phenoxo oxygen atoms.     

Synthesis,Characterization and SOD Activities of IP-copper（Ⅱ）-L-amino Acid Complexes

Four new ternary complexes： [Cu（IP）（L-Val）（H2O）]ClO4·1.5H2O（1）, [Cu（IP）（L-Leu）（H2O）]ClO4（2）, [Cu（IP）（L-Tyr）（H2O）]ClO4·H2O（3） and [Cu（IP）（L-Trp）（H2O）]ClO4·1.5H2O（4） have been synthesized and character/zed by elementa/analysis, molar conductivity, infrared absorption spectroscopy, electronic absorption spectroscopy and cyclic voltammetry, where IP=imidazo[4,5-f][1,10] phenanthroline, L-Val=L-valinate, L-Leu=L-leucinate, L-Tyr=L-tyrosinate and L-Trp=L-tryptophanate. Complex 3 was structurally characterized by X-ray diffraction method, which crystallizes in orthorhornbic space group P21212 in a unit cell of dimensions a=3.0567（4） nm, b=0.74079（9） nm, c= 1.06198（13） nm, V=2.4047（5） nm^3, Z=4,μ=0.1084 cm^-1. The SOD-like activities of catalytic disrnutation of superoxide anions （O2^-· ） by the complexes were determined by means of modified nitroblue tetrazolium （NBT） photoreduction. The IC50 values of complexes 1, 2, 3 and 4 are 0.072, 0.147, 0.429 and 0.264 μmol·L^-1, respectively     

Synthesis,Characterization, and Properties of Supported Tungstozincate Bridged by Co（Ⅱ） Complex Fragment

[Co^11（phen）3]2[{（ZnW12O40）Co^11（phen）2（H2O）}2Co^11（trien）2（NaH2O）2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{（ZnW12O40）Co（phen）2（H2O）}2Co（C6H18N4）2·（NaH2O）2]^4- in which each supported Keggin anion [（ZnW12O40Co^11（phen）2（H2O）]^4- acts as a ligand to coordinate to central bridging Co^2＋ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction（0=-46.796 K）.     

Synthesis and Characterization of New Macrocyclic Cu（Ⅱ） Complexes from Various Diamines, Copper（Ⅱ） Nitrate and 1,4-Bis（2-formylphenoxy）butane

Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis（2-formylphenoxy）butane with diamines and Cu（NO3）2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu（Ⅱ） complexes were found to be 1 ： 1. The Cu（Ⅱ） complexes are 1 ： 2 electrolytes as shown by their molar conductivities （∧m） in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu（Ⅱ） complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.     

Synthesis and Crystal Structure of a New 2D Honeycomb—like Cadmium （Ⅱ） Complex with Tripodal Ligand

A new cadmium (II) coordination polymer, [Cd(TTTMB)₂]‐(SO₄) · 21H₂O, where TTTMB =1,3, 5‐tris (imidazol‐1‐yl‐methyl)‐2,4,6‐trimethylbenzene, was obtained by self‐assembly of tripodal ligand TTTMB with CdSO₄·2.7H₂O in acetonitrile, and characterized by X‐ray crystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a = 1.16891(4) nm, b=2.06671(6) nm, c = 2.48185(7) nm, β = 97.8560(10)°, R = 0.0487, wR = 0.1211. The results of structure analysis indicate that each TTTMB ligand coordinates three metal atoms and in turn each Cd(II) atom with octahedral coordination geometry connects six nitrogen atoms of imidazole group from six different TTTMB ligands to produce a 2D honeycomb network structure. There are a lot of water molecules linked by hydrogen bonds and occupied the channels formed intra‐ and inter‐sheets.     

Samarium （Ⅱ） Diiodide Induced Polarity Inversion of π—Allyl Palladium Complexes：The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(O)-Sml2 in the presence of ArsCbR to from corresponding allylic selenides in good yields.     

Synthesis of Nonionic Oligomeric Manganese（ Ⅱ ） Complexes and Investigation of Their Toxicity and T1 -Relaxation Enhancement

Six nonionic oligomeric manganese （ Ⅱ ） complexes with oligomeric phosphate-polyglycol-EDTA ester ligands were synthesized and characterized. The longitudinal relaxivities of these complexes were measured. One of these complexes, which showed the highest relaxivity, was chosen to be used in the acute toxicity test and the T1-weighted imaging experiment. It has been found that compared to Gd-DTPA, this nonionic oligomeric Mn（ Ⅱ ） complex exhibits no acute toxicity, generates highly enhanced MRI signals and increases the intention time in the rat liver tissue.     

The Synthesis and Absorption Character of New Bis（dithiobenzil）nickel Complex NIR Dyes

A series of new NIR dyes bearing 4-(4-morpholinyl) phenyl and substituted phenyl,were synthesized. The maximum absorption wavelengths of these dyes range from 928nm to 990nm.     

固载于硅胶上的两种N—乙酸取代大环与Co（Ⅱ）,Ni（Ⅱ）,Cu（Ⅱ）,Zn（Ⅱ）的配位

将两种Ｎ－乙酸取代氮氧杂大环固载（键合）于硅胶上，制得了硅胶固载大环（ＳＧＢＭＣ）。研究了它们与Ｃｏ（Ⅱ），Ｎｉ（Ⅱ），Ｃ（Ⅱ），Ｚｎ（Ⅱ）的配位性能，容量、选择性以及ＳＧＢＭＣ的再生。结果表明它们对Ｃｕ（Ⅱ）有良好的配位选择性，且配位后的金属离子易为稀盐酸洗脱，ＳＧＢＭＣ至少可重复使用５次。     

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a = 15.022(3), b = 14.242(3), c = 28.922(6) , β = 98.944(4)o, V = 6112(2) 3, Z = 4, Dc = 1.339 g/cm3, the final R = 0.0860 for 21906 observed reflections with I 2(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861(13), b = 20.838(4), c = 28.274(6) , V = 3644.6(13) 3, Z = 4, Dc = 1.310 g/cm3, the final R = 0.0642 for 11106 observed reflections with I 2(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.