Photolysis of oxygen saturated ethers in the presence of Sn(Ⅱ) or Cu(Ⅱ) salts

Photolysis of diethyl ether-oxygen charge transfer complex in the presence of Sn(Ⅱ)or Cu(Ⅱ)salts gave higher yields of the oxidation products,ethyl acetate,acetaldehyde,ethanol,ethyl formate and methanol compared with those without the salts.In addition,the photolysis of an oxygen saturated te-trahydrofuran(THF)or dibutyl ether solution gave y-butyro-lactone or butanol and butyl butyrate as major products with small amounts of undetermined compounds,respectively.Their yields were also affected by the addition of Cu(Ⅱ)or Sn(Ⅱ)salts.     

含酚氧桥的新型Cu(Ⅱ)-Mn(Ⅱ)和Cu(Ⅱ)-Co(Ⅱ)配合物的合成和磁性

合成了3种新型配合物[Cu(samen)Mn(NO_(2-)Phen)_2](1)、[Cu(sampn)Mn(NO_(2-)Phen)_2](2)和[Cu(samen)CO(terp)](3)(samen~(4-)、sampn~(4-)、NO_(2-)Phen和terp分别表示N,N′-乙二水杨酰胺根阴离子、N,N′-1,2-丙二水杨酰胺根阴离子、5-硝基-1,10-菲绕啉和联三吡啶),测得配合物的变温磁化率,求出交换积分,J分别为-63cm~(-1)(1)、—65cm~(-1)(2)和—7.68cm~(-1)(3),表明金属离子间有反铁磁超交换作用。     

Cu(Ⅱ)Fe(Ⅲ)Cu(Ⅱ)异三核配合物的合成及表征

合成了三种以草酸根为桥联配体的异三核配合物。经元素分析、红外光谱、电子光谱、摩尔电导及室温磁矩对配合物的组成和结构进行了表征。研究表明 ,在Cu(Ⅱ ) Fe(Ⅲ ) Cu(Ⅱ )离子间存在着反铁磁相互作用。     

含草酰胺桥的Cu(Ⅱ)-Fe(Ⅱ)和Cu(Ⅱ)-Zn(Ⅱ)双核配合物的合成、磁性及生物活性

抗菌活性;含草酰胺桥的Cu(Ⅱ)-Fe(Ⅱ)和Cu(Ⅱ)-Zn(Ⅱ)双核配合物的合成、磁性及生物活性     

New Ni(Ⅱ)Cu(Ⅱ)Ni(Ⅱ) trinuclear complexes with an S=3/2 high-spin ground state

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Synthesis and characterization of a tetranuclear copper(Ⅱ) complex with a chiral Schiff base ligand

The title complex l-[Cu^Ⅱ₄（Hvap）₂（vap）₂（MeOH）₂]（CIO₄）₂ 1 has been synthesized and characterized by EA. IR,TGA,solid-state CD spectra and X-ray single-crystal analyses（l-H₂vap’.a Schiff base ligand derived from the condensation of o-vanillin and l-2-amino-3-phenyl-l-propanol）.Complex 1 crystallizes in monoclinic system,chiral space group P2₁ with a =10.4257（18）.b = 21.695（4）,c = 15.721（3）A,β= 94.443（3）.V= 3545.1（11） ³,Z=2,Cu₄C₇₀H₇₈N₄O₂₂Cl₂.Mr= 1652.42,D_c= 1.548 g/cm³, F（000）= 1704 andμ（MoKα） = 1.338 mm^-1.The final R = 0.0682 and wR = 0.1420 for 6170 observed reflections with I > 2σ（I） and R = 0.1775 and wR = 0.1830 for all data.The structure of complex 1 contains a boat-shaped(Cu₄O₄} motif.The solid-state CD spectra confirm the chiral nature of complex 1.     

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.     

The specific detection of Cu(Ⅱ) using an AIE-active alanine ester

Cu(Ⅱ) detection is important because it plays crucial role in several biological processes and ecological systems.Fluorescent techniques have attracted more and more attention in Cu(Ⅱ) detection.In this report,we contribute a novel strategy to use fluorescence spectroscopy for Cu(Ⅱ) specific detection.The specificity relies on the fact that,of the many metal cations,only Cu(Ⅱ) can catalyze the hydrolyzation of a-amino acid ester.The novelty originates from the unique aggregation-induced emission(AIE) property of the fluorescent label.We designed a model a-amino acid ester(TPE-Ala) constructed with alanine and tetraphenylethene-functionalized methanol(TPE-methanol).In comparison with the precursor TPE-Ala, TPE-methanol has lower solubility and is easy to form aggregates in water,thereby displaying a higher fluorescent response.Thus,the Cu(Ⅱ) catalyzed hydrolyzation can be monitored by recording the fluorescence enhancement and fluorescent detection Cu(Ⅱ) is rationally achieved.     

ESR spectra studies of Cu(Ⅱ) 2,4-dihydroxybenzaldehyde tyrosine complex

A novel Schiff base derived from 2,4-dihydroxybenzaldehyde and tyrosine and its copper(Ⅱ)complex have been synthesized and characterized.The composition of the complex is K[CuL] H2O,where L=H11C16NO5.ESR spectra of the copper(Ⅱ)complex were investigated at different temperatures and in various solvents.The second order effect and the relaxation effect were observed in the solution spectrum at room temperature,which was satisfactorily explained by spin Hamiltonian.The bonding parameters of copper(Ⅱ)complex were calculated using spectral parameters from ESR spectra at low temperature.Its bonding characterization and stability were disscussed.The result shows that the in-plane a-bond and the in-plane π-bond in the complex all play an important role.     

Concise Synthesis of(±)-epi-Chrysotricine

Chrysotricine 1 was isolated from the Chinese herb medicine Hedyotis Chrysotricha and was shown to possess antitumor activity1. Its structure has been elucidated as a novel zwitterionic (-carboline alkaloid containing a 2,2,5-trisubstituted tetrahydrofuranyl group. The (-carboline compounds have attracted considerable attraction in recent years because of their promising and intriguing biological activities2. Recently, we have established the absolute configuration of chrysotricine by the fir…     

N,N′-乙二水杨酰胺合铜(Ⅱ)酸根的Cu(Ⅱ)-Co(Ⅱ)配合物的合成与磁性

本文报道了2个新的Cu(Ⅱ)-Co(Ⅱ)双核配合物的制备。经元素分析和红外、电子光谱以及变温磁化率的测定,研究了配合物的某些性质。     

Cu(Ⅱ)-桑色素-十六烷基三甲基溴化铵荧光体系测定微量Cu(Ⅱ)的研究

在H2SO4介质中,以十六烷基三甲基溴化铵(CTMAB)为增敏剂,微量Cu(Ⅱ)对桑色素的荧光具有明显的增强作用,据此建立了测定微量Cu(Ⅱ)的新方法。当最大激发波长和发射波长分别为417nm和497nm时,Cu(Ⅱ)在4.0~20ng/mL浓度范围内与桑色素荧光强度变化值(△F)呈线性关系,其检出限为0.39ng/mL。对12ng/mL Cu(Ⅱ)进行12次平行测定,相对标准偏差为0.76%。方法可用于不同环境水样中微量Cu(Ⅱ)的测定,回收率在96.1%~102.9%之间。     

磁场强化苯甲醛希夫碱吸附Cu(Ⅱ)

研究了磁场作用下,壳聚糖与苯甲醛的合成产物苯甲醛希夫碱(SB-1)对Cu(Ⅱ)的吸附特性,讨论了磁场强度、磁场处理时间、Cu(Ⅱ)溶液的酸度等因素对吸附结果的影响。结果表明,400kA/m的磁场处理前后,壳聚糖和希夫碱对Cu(Ⅱ)的吸附率分别最少增加了4.86%和2.37%,吸附量分别最少增加了0.1459mg/L和0.07111mg/L,而达到吸附饱和的时间均缩短了40%。用经典的等温方程对壳聚糖和希夫碱对Cu(Ⅱ)的吸附平衡数据进行拟合,结果表明,吸附行为与Langmuir和Freundlich两种吸附等温方程式均有较好的相关性。本研究揭示了适当的磁场处理可强化壳聚糖及苯甲醛希夫碱对Cu(Ⅱ)的吸附。     

含草酰胺桥的新型Cu(Ⅱ)—Ln(Ⅲ)—Cu(Ⅱ)三核配合物的合成和磁性

合成了五个以草酰胺为桥联的新型三核配合物[Cu(oxpn)]2Ln(SCN)_3·xH_2O,oxpn为N,N′-二(3-氨丙基)草酰胺根阴离子,Ln为Pr,Nd,Gd,Tb,Dy。测定了[Cu(oxpn)]_2Gd(SCN)_3·1.5H_2O的变温磁化率,求出交换积分J(Cu-Gd)为1.12cm~(-1)和J(Cu-Cu)为-1.62cm~(-1)。表明,Cu(Ⅱ)和Gd(Ⅲ)离子间有弱的铁磁性超交换作用。     

草酰胺基桥联的新型Cu(Ⅱ)-Co(Ⅱ)配合物的合成和性质研究

合成了3种新型配合物[Cu(oxpn)Co(L)_2]·(CIO_4)_2·xH_2O。[Oxpn为N,N′-二(3-氨丙基)草酰胺基阴离子;L为2,2′-联吡啶(bpy)、1,10-菲绕啉(phen)和5-硝基-1,10-菲绕啉(NO_2-phen);x=1,2]。经元素分析、IR、电导和电子光谱等方法,推定配合物具有扩展的草酰胺桥结构,Cu(Ⅱ)及Co(Ⅱ)的配位环境分别为平面四方和八面体构型。配合物的变温磁化率已测(4.2～300K)。其数值已用最小二乘法与从自旋哈密顿算符导出的磁方程拟合,求得交换参数J为-22.36 cm~(-1)(bpy),-15.45 cm~(-1)(phen)和-19.10 cm~(-1)(NO_2-phen),表明金属离子间有较弱的反铁磁交换作用。     

Cu(Ⅱ)、Zn(Ⅱ)Schiff碱配合物的合成及其光热性质

用5-硝基水杨醛与色氨酸缩合制备了一种Schiff碱配体,将其与过渡金属Cu(Ⅱ)、Zn(Ⅱ)进行作用合成出两种新型的配合物.采用元素分析、差热-热重、IR、UV、摩尔电导率等对配体和配合物进行了表征,并测定了化合物的荧光性质和对超氧离子的催化歧化作用.     

μ-草酰二胺Cu(Ⅱ)-Fe(Ⅱ)双核配合物的合成与磁性

合成和表征了两种含草酰胺桥的新型异双核配合物［Cu(oxae)Fe(tmen)₂］SO₄(a)和［Cu(oxpn)Fe(tmen)₂］SO₄(b)。变温磁化率(4～300K)测量和磁分析表明两个Cu(Ⅱ)-Fe(Ⅱ)双核配合物中金属离子间有中等强度的反铁磁超交换作用。     

Synthesis and properties of the copper(Ⅱ) complexes with stable radical

Four novel copper(Ⅱ) complexes have been synthesized,namely Cu(hfac)2NITPhNO2 (1),Cu(hfac)2NITPhCH3 (2),Cu(pfpr)2NITPhNO2,(3) and Cu(Pfpr)2NITPhCH3 (4),where hfac= hexafluoro-acetylacetonate,pfpr=pentafluoropropionate,NITR.=2-R-4,4,5,5-tetraniethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide.(R=4-nitrophenyl,4-methylphenyl).These complexes were rharicter-ized by elemental analyses,IR,electronic spectra and molar conductance.The temperature-dependent magnetic susceptibility of complexes 1 and 3 have been studied in the 4 300 K range,giving I he exchange integral J=10.56 cm-1 for complex 1 and J =-30.9 cm-1 for complex 3.     

Trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes bridged by μ_3-carbonato anion

The trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes [(CuTPA)_3(μ3-CO_3)] (ClO_4)_4(1) and [(ZnTPA)_3(μ_3-CO_3)] (ClO_4)_4 (2) (TPA=tri(pyridylmethyl) amine) have been synthesized. X-ray structure analysis of the two complexes proves that CO_3~(2-) anion has an unusual triply bridging ligand, bridging three CuTPA and ZnTPA units respectively, and assembles new trinuclear complexes. The CO_3_(2-) comes from atmospheric CO_2. The structure of each trinuclear unit consists of three copper or zinc atoms in a five-coordinate triangular bipyramidal environment. The [(CuTPA)_3 (μ_3-CO_3)] (ClO_4)_4 compound shows a very weak antiferromagnetic coupling.     

Application of Fast Radical Rearrangement in the Mechanistic Investigation of Intramolecular C-H Insertion by Rh(Ⅱ)-Mediated Carbenoids

IntramolecularC-HinsertionbyRh(II)-mediatedcarbenoidhasbecomeareactionofconsiderableimportanceinrecentyears'.InadditiontoitsnumeroussyntheticaPplications',therehavebeenextensiveinvestigationsonthemechanismofthisreaction3.AlthoughithasbeengenerallybeIievedthattheC-Hinsertionproceedsthroughaconcertedmechanism,thesuspicionexistSthatradicalorionicpairsndghtbeinvolvedinthereaction.Forexample,DoyIe"andPirrung,'reportedthattheC-HinsertionscatalyzedbyRh2(O2CCF3)4proceededwithstatisticalproduct…