μ-σ,π-苯乙烯基铁硫配合物亲核取代反应的研究——某些三苯膦或三苯胂μ-σ,π-苯乙烯基铁硫配合物的合成及结构

(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_6和PPh_3或AsPh_3在苯中回流可分别制得(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_5和PPh_3(R=Et,Bu~t,CH_2=CHCH_2)和(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_5AsPh_3(R=Et,Bu~t).经X-射线衍射法测得(μ-σ,π-PhCH=CH)(μ-Bu~tS)Fe_2(CO)_5AsPh_3的单晶结构.该晶体属三斜晶系.空间群P1.晶胞参数:a=10.196(2),b=11.62(2),c=15.814(3)(?);α=102.41(1),β=91.38(2),γ=112.93(1)°;V=1673.1(?)~3,D_c=1.49g·cm~(-3),Z=2.     

混合配体构筑的Cd~(2+)配合物的合成及其晶体结构

通过溶剂热技术,制得一种新型的Cd~(2+)配合物[Cd(L)_2(ba)_2]_2(1,L=4'-(4-甲基苯)-4,2':6',4″-三联吡啶,Hba=苯甲酸),其结构经IR,元素分析和单晶射线衍射表征。1属单斜晶系,空间群为P2_1/c,晶胞参数a=1.095 5(2)nm,b=1.404 1(3)nm,c=3.045 5(8)nm,β=103.37(3)°,V=4 557.6(18)3,D_c=1.459g·cm~(-3),Z=2,R_1=0.045 5,wR_2=0.094 0[I2σ(I)]。结构分析表明:1为零维双核结构,通过π…π堆积作用拓展为二维层状超分子。     

The polarization dependent differential cross sections of the reactions:H+LiH~+(v=0,j=0)→H_2+Li~+ and H~++ LiH(v=0,j=0)→H_2~++Li

<正>Quasi-classical trajectory(QCT) calculations have been carried out to study the generalized polarization dependent differentialcross sections(PDDCSs) for the reactions H + LiH~+(v = 0,j = 0)→H_2 + Li~+ and H~+ + LiH(v = 0,j = 0)→H_2~+ + Li occurring onthe two lowest-lying electronic states of the LiH_2~+ system,using the ab initio potential energy surfaces(PESs) of Martinazzo et al.[3].Four PDDCSs,i.e.,(2π/σ)(dσ_(00)/dω_t),(2π/σ)(dσ_(20)/dω_t),(2π/σ)(dσ_(22+)/dω_t),(2π/σ)(dσ_(21-)/dω_t) have been discussed in detail.     

论文选摘

理论塔片高度(H.E.T.P.)与溫度的关系气相色谱学中理论塔片数n=t_R~2(σ_1~2+σ_2~2)~(-1),其中σ_1~2=2D_gLu~(-3),σ_2~2=2β~2F_1~2L(αF_gK~2u)~(-1)。(t_R为校正保留时间,D_g气相扩散常数,L色谱柱长,u载气线速,α气相溶入液相的速率常数或吸附速率常数,F_l,     

配盐[(μ-PhSe)(μ-CO)Fe~2(CO)~6][Et~3NH]的亲电反应研究: (μ-苯硒)(μ-酰基)及(μ-苯硒)(μ-烯基)六羰基二铁配合物的合成及结构

本文研究由Fe_3(CO)_12,PhSeH,Et_3N所形成的配盐[(μ—PhSe)(μ—CO)Fe_2(CO)_6][Et_3NH]与对甲氧基苯甲酰氯、乙酰氯、丙酰氯、苯乙酰氯、α-甲基丙烯酰氯、巴豆酰氯、肉佳酰氯、苯乙炔和β-溴代苯乙烯的反应和机理,合成八个既含μ-苯硒又含μ-酰基或μ-烯基配体的六羰基二铁配合物除用元素分析,MS、IR、~1H NMR表征它们的结构外,尚测得(μ-PhSe)(μ-σ,π-PhCH=CH)Fe_2(CO)_6的单晶结构.该分子单晶的空间群为P2_1/c,晶胞参数α=0.9236(2),b=1.0966(3),c=2.0348(6)nm,β=101.53(1)°,D_x=1.77g/cm~3、Z=4,R=0.054,R_W=0.061     

醋酸乙烯酯基桥连铁硫配合物(σ,π-μ-CH3CO2C=CH2)(μ-RS)Fe2CO)6的制备及结构鉴定

乙酰氯同Fe_3(CO)_(12),RSH,Et_3N所形成的盐[(μ-CO)(μ-RS)Fe_2(CO)_6]Et_3NH相作用,生成一类含醋酸乙烯酯基配体的桥连铁硫配合物(σ,π-μ-CH_3CO_2C=CH_2(μ-RS)Fe_2(CO)_6[R=Et,tert-Bu,Ph)。除用碳氢分析,IR,~1HNMR及X衍射技术表征这类配合物的结构和构象外,还对形成此类产物的过程进行了初步讨论。R=Ph配合物单晶的空间群为PI,晶胞参数a=7.087(3),b=8.824(2),c=15.740(3),α=76.20(1),β=88.15(2),γ=86.28(2)°,D_x=1.65g·cm~(-3),Z=2。醋酸乙烯酯基配体中带有醋酸根的硫与一个铁原子发生σ相互作用,而碳-碳双键与另一个铁原子则发生π相互作用。Fe—Fe键长为2.553(1))苯基与硫桥原子以e键相连。     

A Novel Zn(Ⅱ)Complex with 1D Supramolecular Water Tape Formed by Cyclic Tetrameric Water Clusters

<正>A new mixed-ligand Zn(Ⅱ)complex,[Zn(4,4'-bipy)_2(H_2O)_4]·2ANS·6H_2O(1,4,4'- bipy=4,4'-bipyridine,HANS=2-aminonaphthalene-1-sulfonic acid),has been isolated and structurally characterized by single-crystal X-ray diffraction,FT-IR spectrum,TG and elemental analysis.It crystallizes in the monoclinic system,space group P2_l/c with a=12.4852(8),b= 18.3163(12),c=10.9707(7)(?),β=114.2600(10)°,V=2287.3(3)(?)~3,D_c=1.455 g/cm~3,M_r= 1002.37,Z=2,F(000)=1048,μ=0.704 mm~(-1),the final R=0.0408 and wR=0.962 for 4029 observed reflections with I2σ(I).Interestingly,an unusual one-dimensional(1D)water tape with cyclic tetrameric water clusters can be observed in 1,which are further trapped via Zn-O coordination bonds exhibiting a 2D Zn(Ⅱ)-water layer.These 2D Zn(Ⅱ)-water layers are stacked together into a 3D interdigitated supramolecular architecture via weakπ…πinteractions,in which free ANS anions are tightly filled by hydrogen-bonding interactions.Thus,π…πand classical hydrogen-bonding interactions are found as main driving forces to stabilize the 2D Zn(Ⅱ)-water layers.     

HRh[(C_6H_5)_2PCH_2CH_2P(C_6H_5)_2]_2的晶体和分子结构

HRh[(C_6H_5)_2PCH_2CH_2P(C_6H_5)_2]_2(分子量900.8)晶体属单斜晶系,空间群P21/n,晶胞参数a=21.319(2),b=20.844(2),c=10.130(3),β=91.255(2)°,V=4500.4,Z=4,D_c=1.15g·cm~(-3),F(000)=1864,μ(CuKα)=44.97cm~(-1)。共收集独立衍射点数7636个,其I>3σ(1)的衍射点数6810个。最终的R=0.045,R_w=0.050(W=1/σ~2(F)+(F)+g|F|~2)。其分子结构呈畸变的三角双锥构型。     

过渡金属双核化合物Cr_2(O_2CH)_4、Mo_2(O_2CH)_4及CrMo(O_2CH)_4的从头计算研究

用从头计算方法研究双核过渡金属化合物Cr_2(O_2CH)_4、MO_2(O_2CH)_4及CrMo(O_2CH)_4的金属—金属多重键性质,计算优化键长与实验值符合很好,原子布居表明Mo_2(O_2CH)_4和CrMo(O_2CH)_4中Mo—Mo、Cr—Mo键分别为σ~2π~4δ~2与σ~2δ~2π~4四重键,同时金属-d与氧和碳-p电子间的电荷重叠对分子稳定有相当贡献。对Cr_2(O_2CH)_4在优化键长下3种组态σ~2δ~2δ~(*2)σ~(*2)、π~4π~(*4)及σ~2δ~2π~4的电子结构、原子布居、总能量及电离能的计算进行比较,讨论了Cr—Cr的成键性质,指出描述Cr—Cr间金属多重键本质必须考虑电子相关效应的影响。     

基于2-吲哚甲酸的铁(Ⅱ)和镉(Ⅱ)配合物的合成与晶体结构（英文）

采用水热方法,以2-吲哚甲酸(2-HINDF)为主配体,2,2’-联吡啶(2,2’-bpy)、1,10-邻菲罗啉(phen)为辅配体分别与碳酸铁和碳酸镉反应,合成了2个配合物[Fe(phen)_3](2-INDF)_2·8H_2O(1)和[Cd_4(2,2’-bpy)_8(2-INDF)_8]·7H_2O(2),利用元素分析、红外光谱、X-射线单晶衍射以及热重分析对其结构进行了表征。X-射线单晶衍射分析表明,配合物1晶体为单斜晶系,属于P2_1/c空间群,晶胞参数为a=12.995(3)?,b=31.842(6)?,c=13.073(3)?,β=110.23(3)?,V=5075.6(18)?~3,Mr=1060.89,Dc=1.388 g/cm~3,F(000)=2216,μ=3.70 mm~(-1),Z=4,最终偏离因子[Iσ(I)]R_1=0.0601,wR_1=0.1649。配合物2晶体为三斜晶系,属于P-1空间群,晶胞参数为a=13.276(3)?,b=13.591(3)?,c=21.764(4)?,α=78.77(3)?,β=80.87(3)?,γ=67.99(3)°,V=3555.2(13)?~3,Mr=3106.41,Dc=1.451 g/cm~3,F(000)=1582,μ=6.68 mm~(-1),Z=1,最终偏离因子[I2σ(I)]R_1=0.0629,wR_1=0.1753。     

分散体系中任意形状的胶粒模型与相互作用能——Ⅱ、不等同球颗粒

鉴于不等同球颗粒在胶体化学中的重要性,所以它一直引起人们在理论上的关注。Hogg、Healy和Fuerstenau(HHF)对Poisson-Boltzmann方程引用Debye-Hückl近似,得出不同平行平板型颗粒在恒电位表面时相互作用能计算公式,进而HHF用Derjaguin法得出不等同球颗粒相互作用能的表达式。虽然HHF的公式仅适用低电位的情况,但它的表达式特别简单,因而一直被广泛使用。Ohshima等(OCHW)对球颗粒做了曲率校正,Barouch等(BM)对Poisson-Boltzmann方程提出二维解法,使不等同球颗粒的相互作用能的计算有了改进和提高。本文根据我们提出的模型和方法,对HHF公式也做了曲率校正,结果表明它和OCHW的曲率校正结果相当,但它的表达式却要简单得多。     

VA族元素氢化物的紫外光解和多光子电离Ⅲ. AsH3分子的紫外激光光解和多光子电离

通过193 nm的ArF激光光解AsH_3, 首次在420-650 nm之间观察到了AsH_2(Ã ~2A_1→X ~2B_1)的发射光谱。经过认证之后, 获得了v=19928+868v′_2-3v′_2~2-(989v″_2-6v″_2~2)的经验公式, 并辨认了七个谱带系。AsH_2(Ã ~2A_1)的辐射寿命是(130±20)ns。此外, 还观察到四条As(5s→4p)的原子发射谱线和多光子电离信号。     

配位聚合物{Zn[(BTDC)_2(DMF)_2]}_4·(DMF)_4的合成及其晶体结构

2,2′-联二噻吩-5,5′-二羧酸(H2BTDC)与硝酸锌经水热合成制得新型配位聚合物{Zn[(BTDC)2(DMF)2]}4.(DMF)4(1),其结构经X-射线单晶衍射和元素分析表征。1属单斜晶系,空间群P2(1)/c,晶胞参数a=6.5913(13),b=22.813(5),c=16.315(3),V=2 450.5(9)3,Z=4,F(000)=1 112,cρalcd=1.455 g.cm-3,R1=0.040 2,wR2=0.082 4[I2σ(I)]。晶胞中每个锌原子与两个配体、两个配位的DMF溶剂分子和一个自由的DMF分子配位,共同组成zigzag一维链状结构。     

Synthesis and Crystal Structure of 1,4,7,10-Tetrakis （2-（（4-hydroxy）phenoxy）ethyl）-1,4,7,10- tetraazacyclododecane

A novel molecule tetra-N-alkylation of cyclen （1,4,7,10-tetraazacyclododecane）, 1,4,7,10-tetrakis（2-（（4-hydroxy）phenoxy）ethyl）-1,4,7,10-tetraazacyclododecane 2, was synthesized and structurally characterized by single-crystal X-ray diffraction. The molecule turned into chiral helical compound crystals grown from EtOH by slow diffusion at room temperature and three of the four hydroquinone groups of the benzene ring formed a g-electron-rich cavity by C-H…π stacking interaction. The crystal belongs to the monoclinic system, space group P21/C with a = 13.9192（9）, b = 13.2871（6）, c = 22.1894（15）A^°, β = 91.4600（10）°, V = 4102.5（4）A^°3, Z = 4, Dc = 1.219 g/cm^3, C40H52N4O8, Mr = 752.89, F（000） = 1616,μ = 0.088 mm^-1, MoKa radiation （λ = 0.71073）, R = 0.0578 and wR = 0.1389 for 5588 observed reflections with I 〉 2σ（I）. Moreover, compound 2 was characterized with ^1H NMR, ^13C NMR, IR spectra and MS.     

8-取代苯乙烯基-10，10-二甲基-10H-吡啶并[1，2-a]吲哚盐的紫外和荧光光谱

The UV and FL spectra of the title compounds were reported and substituent effects of them were discussed in this work. Fairly good correlations between λ_(max)~(uv) and Δσ(σ_p-σ_m), λ_(max)~(FL) and σ_p~+(or σ_m~+), stokes shift values and Δσ were established respectively.It showed that the electron effects of the substituents played a main role Spectra sensitivity toward N(CH_3)_2 and OH substituted compounds were also studied.     

Synthesis and Structure of Di－μ－chlorobis（di－tert－butylcyclopentadienyl） Erbium Chloride

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆＤｉ－μ－ｃｈｌｏｒｏｂｉｓ（ｄｉ－ｔｅｒｔ－ｂｕｔｙｌｃｙｃｌｏｐｅｎｔａｄｉｅｎｙｌ）ＥｒｂｉｕｍＣｈｌｏｒｉｄｅＲＥＮＪｉｎ－Ｓｏｎｇ；ＳＨＥＮＱｉ；ＨＵＪｉｎｇ－Ｙｕ；ＬＩＮＹｏｎｇ－Ｈｕａ；ＸＩ...     

液相色谱双保留机理动力学过程研究

本文根据质量平衡原理建立了反相色谱双保留机理的质量平衡模型, 导出了色谱流出曲线的一阶矩和二、三阶中心矩, 获得了双保留机理色谱容量因子和塔片高度的表达式. 讨论了各种色谱动力学参数对柱效和峰形的影响, 对改善色谱峰对称度和提高柱效的措施作了理论说明。     

Synthesis and Crystal Structure of a Heterometallic Chain Coordination Polymer:{[Ni_2Mn_2L_2(CH_3CH_2OH)(H_2O)]·CH_3OH·2H_2O}_n

A chain-like coordination polymer with the chemical formula of {[Ni2Mn2L2(CH3CH2OH)-(H2O)]·CH3OH·2H2O}n has been synthesized by the assembly reaction of K2NiL·H2O and Mn(OAC)2·4H2O with a 1:1 mole ratio in methanol,where OAC-=CH3COO-and H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl}imino)methyl]benzoic acid.The crystal structure was determined by single-crystal X-ray diffraction analysis.It belongs to the triclinic system,space group P1,with a=9.9464(8),b=13.4718(11),c=14.3877(12),α=87.1930(10),β=85.4280(10),γ=74.6470(10)°,V=1852.4(3)3,Z=2,Dc=1.807g/cm3,Mr=1008.03,λ(MoKα)=0.71073,μ(MoKα)=1.794 mm-1,F(000)=1032,R=0.0527 and wR=0.1284(Ⅰ2σ(Ⅰ)).The compound exhibits a chain-like structure formed by dissymmetrical tetranuclear units.     

取代羧酸pKa的分子树拓扑研究

基于非氢原子i的酸性点价(δai)建构分子树拓扑指数(mT)及其分支指数(mTC)和叶指数(mTx),并提出表征诱导效应的叶指数(mT′x).通过最佳变量子集算法获得38种羧酸的pKa与0TC、1TC、0T′x的回归方程:pKa=3.0352-1.25700T′x-0.15540TC+0.07811TC,R=0.9766.通过Jackknife法检验,该模型具有总体稳健性.优于文献的七元最佳回归模型(R=0.957),与其分子力学方法(CoMFA)结果(R=0.988)较为接近.结果表明,所建拓扑指数是合理的,具有科学性基础.