配合物RuCl2(bdpx)(NHCH2CH2NH2)的合成及其催化活性

合成了一种新的双膦-钌-二胺配合物--RuCl2(bdpx)(NH2CH2CH2NH2)[bdpx=邻-二(二苯基膦)二甲苯](1),并研究了1催化苯乙酮(2)的加氢反应.在1 0.002 mmol,n(2):n(Me3COK):n(1)=10 000:120:1,氢气压力为3 MPa的条件下,于70℃反应4 h,2的转化率达100%.     

Syntheses and Characterizations of （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 and （NH3CH2CH2NH3）2Bi2I10

The title compounds have been respectively synthesized by solution process and solvothermal reaction, and their crystal structures were determined by X-ray diffraction method. For （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 1, it crystallizes in tficlinic, space group P1^- with Mr = 2049.76, a = 8.5719（1）, b = 11.7461（3）, c = 15.700（1）A, V = 1451.4（1）A^3, Z = 1, Dc = 2.345 g/cm^3, F（000） = 924, μ（MoKα） = 8.907 mm^-1, T = 293（2） K, the final R = 0.0655 and wR = 0.0804 for 2399 observed reflections with I 〉 2σ（I）. For （NH3CH2CH2NH3）2Bi2I10 2, it crystallizes in monoclinic, space group P21/n with Mr= 1811.20, a = 8.434（4）, b = 13.862（6）, c = 13.362（6）A, V = 1499.9（12）A^3, Z = 2, Dc = 4.010 g/cm^3, F（000） = 1536,μ（MoKα） = 22.007 mm^-1, T = 293（2） K, the final R = 0.0584 and wR = 0.1451 for 1798 observed reflections with I 〉 2σ（I）. The structures of 1 and 2 contain halobismuthate monomer and dimers, respectively. It is noteworthy that the dimers and their organic counters in 2 connect each other by N…I hydrogen bonds to form a layered structure, and the electrostatic interactions and crystal packing forces between layers give rise to the packing of the crystal. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.13 and 2.01 eV, respectively.     

Synthesis and Crystal Structure of a 2D Coordination Polymer： [Nd2（PDB）2（CH3COO）2（H2O）3]

A novel coordination polymer [Nd2（PDB）2（CH3COO）2（H2O）3] （H2PDB = pyridine3,4-dicarboxylic acid） has been synthesized by the reaction of Nd（CH3COO）3 with pyridine3,4-dicarboxylic acid under hydrothermal conditions. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the composition and crystal structure of the title complex which belongs to the triclinic system, space group P^-1 with a = 6.9409（14）, b = 7.5497（15）, c = 22.530（5）A, α = 84.79（3）, β = 88.15（3）, γ= 75.55（3）^o, C18H18N2O15Nd2, Mr = 790.82, Z = 2, V = 1138.5（4） A^3, Dc = 2.307 g/cm^3,μ = 4.593 mm^-1, -6≤h≤8, -5≤k ≤8, -26≤l≤ 26, F（000） = 760, Rint = 0.0298, R= 0.0314 and wR= 0.0695 （I〉 2σ（I））. Nd（1） and Nd（2） are linked into zigzag chains by carboxylate groups of acetate with interesting μ3-η^2：η^2 fashion. The zigzag chains are bridged by PDB to form a 2D framework, and a 3D supramolecular network is further constructed via π-π stacking.     

双膦配合物RuCl2(dppe)(NH2CH2CH2NH2)的合成及催化性能研究

合成了双膦配合物RuCl2(dppe)(NH2CH2CH2NH2)[dppe=1,2-二(二苯膦基)乙烷]。考察了此配合物对苯乙酮及其衍生物加氢反应的催化性能,并对各种反应参数变化对加氢反应的影响进行了详细的研究。结果表明,此配合物对苯乙酮的加氢反应具有良好的催化活性,在苯乙酮/(CH3)3COK/配合物的摩尔比为5000:40:1、氢气压力为3 MPa的条件下,于70℃反应5 h,苯乙酮的转化率可达到99.6%。     

(CH2)2N和(CH3)2NH+的密度泛函理论计算

用密度泛函理论UB3LYP／6-31G（d,p）方法研究了二甲胺自由基（CH3）2N及其质子化离子（CH3）2NH 的构象和超精细结构．在由构象研究得到的两种自由基的最稳定结构上,用密度泛函的UB3LYP和UB3PW91方法及从头计算的UHF、UMP2（FULL）方法计算了α-质子、β-质子和N核上的超精细偶合常数A（Hα）、A（Hβ）和A（N）结果表明：两种自由基中甲基内旋转的位垒均很低,分别为0．46kJ·mol-1（（CH3）2NH ）和2．6kJ·mol-1（（CH3）2N）．UB3LYP／6-31G（d,p）和UB3PW91／6-31G（d,p）计算的A（Hα）、A（Hβ）和A（N）与ESR实验结果符合得很好,UMP2／6-31G（d,p）方法的计算值与实验值符合得也较好．     

Synthesis and Structure of a POMs-based 3D Zeolike Ionic Crystal, {[Co（dpdo）2（H2O）2（CH3CN）]2（SiMo12O40）（H2O）2}n

A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.     

Syntheses and Crystal Structures of [Na（H2O）1/2]X and NH2（CH2CH3）2X and Antioxidant Activity of the Former

In order to enhance the water-solubility and biological utilization rate of chrysin, sodium 5,7-dihydroxylflavone-8-sulfonate （1, [Na（H2O）1/2]X, X = C15H9OSO3, 5,7-dihydroxylfla- vone-8-sulfonate） was synthesized and its structure was identified on the basis of NMR, FT-IR and elemental analysis. The assembly of 5,7-dihydroxylflavone-8-sulfonate with diethylamide cation afforded diethylamide 5,7-dihydroxylflavone-8-sulfonate （2, NH2（CH2CH3）2X） which was characterized by FT-IR and elemental analysis. The crystal structures of 1 and 2 were determined by X-ray single-crystal diffraction analysis. The crystal of 1 is of triclinic system, space group P1, with a = 8.5628（13）, b = 12.8916（19）, c = 13.562（2） A, α = 82.494（1）, β = 78.601（2）, γ = 84.033（2）°, C30H20Na2O15S2, Z = 2, Mr = 730.59, V = 1450.3（4） A3, Dc = 1.673 g/cm3, F（000） = 748, p = 0.295 mm^-1, the final R = 0.0641 and wR = 0.1458. The crystal of 2 crystallizes in the triclinic system, space group Pi, with a = 7.689（2）, b = 11.184（3）, c = 11.734（3） A, α = 74.268（3）, βl = 81.751（4）, γ= 87.991（3）°, C19H21NO7S, Z = 2, Mr= 407.43, V= 961.2（4） A3, Dc = 1.408 g/cm3, F（000） = 428, p = 0.210 mm^-1, the final R = 0.0484 and wR = 0.1195. In 1, the three-dimensional structure is organized into organic and inorganic regions; the flavone skeletons are stacked into organic regions by π...π staeking interactions; inorganic regions are generated by Na-O coordination bonds among sulfonate groups, coordinated water molecules and NaI. The sulfonate groups play an important role as a bridge of inorganic and organic regions. One-dimensional chain structure of 2 is extended by N-H…O hydrogen bonds and π...π stacking interactions. Furthermore, the antioxidant activity of 1 was evaluated. The scavenging activity of 1 to DPPH free radical is better than that of the parent compound chrysin.     

（η^5—4,7—Me2—Ind）2Zr（CH2Ph）2／烷基铝催化乙烯齐聚的研究

考察了(η5-4,7-Me2-Ind)2Zr(CH2Ph)2与EtnAlCl3-n(n=2(A),n=1(B),n=1.5(C))所组成的二元催化体系,在不同的反应温度、陈化温度、铝锆比下催化乙烯齐聚的活性和选择性.结果表明,在相同的反应条件下,3种催化体系的催化活性顺序为B>C>A;选择性则相反,为B<C<A.在最佳反应条件下,(η5-4,7-Me2-Ind)2Zr(CH2Ph)2/EtAlCl2二元催化体系对乙烯聚合的催化活性为1912.3g齐聚物/(gZr*h),对C4～10烯烃的选择性为96.6%.     

A density functional theoretical studies on the structures and aromaticities of （CH）n（BCO）6-n （n =0-6）

Density functional theoretical calculations have been made on the electronic structure of （CH）n（BCO）6-n（n = 0-6） at B3LYP/6- 311 ＋ G（d） level. The nuclear-independent chemical shifts （NICS） values calculated using the gauge-including atomic orbitals （GIAO） method were used to assess on the aromaticities of these molecules. The results shows that （CH）n（BCO）6n（n = 0-6） species are aromatic.     

Synthesis and Characterization of Organosilyl Derivatives of Keggin Polyoxometalates [XW11O40（SiR）2]n- CX=CoIII, P; R=CH=CH2, OH）

以CoIIIW11和有机硅烷为原料,在pH=1,乙醇-水（体积比=2∶1）的混合溶剂中,首次合成了Keggin型有机硅取代的钨钴酸盐[CoIIIW11O40（SiR）2]5-（CoIIIW11（SiR）2,R=CH=CH2,OH）.这里,乙醇作为共溶剂增加硅烷在溶液中的溶解度,使CoIIIW11在转化为饱和结构之前能够快速与硅烷相遇并反应.产物的组成和结构用IR,UV-Vis,NMR,TG-DTA,元素分析等技术进行了全面表征.结果显示,两个SiR基团进入了CoIIIW11的空位,并形成Si—O—Si桥,得到与先前报道的硅取代钨硅酸盐和钨磷酸盐相似的结构.还运用此条件成功合成了以往需要在固-液相转移条件下合成的[PW11O40（SiR）2]3-[PW11（SiR）2,R=CH=CH2,OH],进一步证明了此方法在合成有机硅取代的多金属氧酸盐方面的可行性和通用性.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions： [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate, [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O 1, was hydrothermaUy synthesized and characterized by IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system, space group P21/c with a = 16.6073（6）, b = 15.3333（5）, c = 19.9869（7） A, β = 103.41（1）°, Mr = 5481.38, V = 4950.8（3） A3, Z = 2, Dc = 3.677 g/cm^3, F（000） = 4900, μ（MoKa） = 22.165 mm^-1, GOOF = 1.005, the final R = 0.0228 and wR = 0.0527. The crystal structure indicates that the [Co4（H2O）2（B-α-GeW9O34）2]^12- polyoxoanion contains two trivacant Keggin [B-α-GeW9O34]^10- fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement （C2h symmetry） leading to a sandwich-type structure.     

[NiCl（Ph2PCH2CH2OH）2Cl&#183;H2O]^＋Cl^-和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-的合成及晶体结构

通过NiCl2.6H2O与双齿配体2-（二苯基膦）乙醇（Ph2PCH2CH2OH）或其氧化物2-（二苯基氧膦）乙醇[Ph2P（O）CH2CH2OH]的反应,制得两种结构新颖的阳离子型镍配合物[NiCl（Ph2PCH2CH2OH）2（H2O）]^＋Cl^-（1）和[Ni（Ph2P（O）CH2CH2OH）4]^2＋[NiCl4]^2-（2）.通过元素分析、31P核磁共振及X射线单晶衍射对配合物1和2的结构进行了表征.配合物1的晶体属单斜晶系,C2/c空间群,中心金属Ni具有六配位八面体几何构型.配合物2属四方晶系,I4（1）/a空间群,中心原子Ni与P＝＝O基团中的O配位形成平面四边形构型.     

高氮含能配合物M（ATZ）（bpy）m&#183;nH2O液相生成反应的热动力学

合成了6种固态高氮含能配合物M（ATZ）（bpy）m&#183;nH2O（（1）M=Mn,m=2,n=3;（2）M=Co,m=2,n=7;（3）M=Ni,m=2,n=0;（4）M=Cu,m=1,n=0;（5）M=Pb,m=1,n=3;（6）M=Zn,m=1,n=1;ATZ=5,5′-偶氮四唑,bpy=2,2′-联吡啶）。对它们的结构和性能进行了表征。用RD496-CK2000微热量计测定了298.15 K下各配合物的液相生成反应焓变分别为：ΔrHm^θ（1）=241.245&#177;0.060 kJ/mol,ΔrHm^θ（2）=-256.875&#177;0.050 kJ/mol,ΔrHm^θ（3）=-265.172&#177;0.038 kJ/mol,ΔrHm^θ（4）=-236.538&#177;0.038 kJ/mol,ΔrH^θm（5）=-249.698&#177;0.038 kJ/mol,ΔrHm^θ（6）=-185.072&#177;0.048 kJ/mol。通过试验测定得到的所有液相反应的ΔrHm^θ均为负值,有利于目标物生成;并改变反应温度,研究了它们的液相生成反应的热动力学。改变温度研究了液相生成反应的热动力学,利用反应热化学数据和动力学方程结合热动力学实验数据计算了活化焓（ΔH≠^θ）、活化熵（ΔS≠^θ）、活化自由能（ΔG≠^θ）、表观反应速率常数（k）、表观活化能（E）、指前常数（A）和反应级数（n）。     

Impact of Water Molecules on the Isomerization of CH3S（OH）CH2 to CH3S（O）CH3： A Computational Investigation

The isomerization of CH3S（OH）CH2 to CH3S（O）CH3 in the absence and presence of water has been investigated at the G3XMP2//B3LYP/6-311 ＋ G（2df, p） level. The naked isomerization, the reaction without water, gives the high barrier height （21.56 kcal.mol^-1）. Three models are constructed to describe the water influence on the isomerization, that is, water molecules are the catalyst and the microsolvation, and water molecules act as the catalyst and microsolvation simultaneously. Our results show that the isomerization barrier heights of CH3S（OH）CH2 to CH3S（O）CH3 are reduced by 12.32, 11.04, and 7.80 kcal.mol^-1, respectively, when one, two, and three water molecules are performed as catalyst, in contrast to the naked isomerization. Moreover, the rate constants of the isomerization are calculated using the transition state theory with the Wigner tunneling correction over the temperature range of 240-425 K. We find that the rate constant of a single water molecule as the catalyst is 1.58 times larger than the naked isomerization at 325 K, whereas it is slower by 6 orders of magnitude when water molecule serves as the microsolvation at 325 K, compared to naked reaction. So the water-catalyzed isomerization of CH3S（OH）CH2 to CH3S（O）CH3 is predicted to be the key role in lowering the activation energy. The isomerization involving water molecules acting as mierosolvation is unfavorable under atmospheric conditions.     

Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate （n-Bu4N）2 [Mo6O16（OCH3）2 {HOCH2C（CH2O）3}2 {Mn（CO）3}2]

The polyoxoanion incorporated {Mn（CO）3^＋} complex, （n-Bu4N）2[Mo6O16（OCH3）2{HOCH2C（CH2O）3}2·{Mn（CO）3}2]（1）, has been synthesized by the reaction of （n-Bu4N）4[Mo8O26] with Mn（CO）5Br in methanol, in the presence of C（CH2OH）4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1：C25H48MnMo3NO16 （1）, Triclinic Pi, a=0.9405（3） nm, b=1.3351（4） nm, c=1.5455（4） nm, α=103.206（5）°, β=102.165（5）°, γ=100.784（5）°, V=1.7896（9） nm^3, Z=2, R1=0.0703, wR2= 0.1495. The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn（CO）3^＋ units. The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.     

[π-C5H5N（CH2）15CH3]3[PMoW3O24]／H2O2：高效的环境友好且可再生的烯烃环氧化磷钼钨杂多酸催化体系

研究了一种可循环并且环境友好的催化体系：[π-C5H5N（CH2）15CH3]3[PMoW3O24]／过氧化氢／乙酸乙酯／烯烃．此体系不仅可以催化烯烃的环氧化反应,而且避免了对含氯溶剂的使用．反应在过氧化氢／乙酸乙酯的两相体系中进行,可以将多种烯烃转化为相应的环氧化物,且产率较高．此催化剂具有反应控制相转移的特征,反应结束后可以回收再利用．采用Raman,IR,^31P MAS NMR和^31P NMR等手段对新鲜及重复使用过的催化剂进行表征．结果表明：新鲜催化剂[π-C5H5N（CH2）15CH3]3[PMoW3O24]是一种混合物,含有多种过氧磷钼钨酸盐,如{PO4[MoO（O2）2]4}^3-,[（PO4）{Mo3WO20}]^3-,[（PO4）{Mo2W2O20}]^3-,[（PO4）{MoW3O20}]^3-和{PO4[WO（O2）2]4}^3-．当过氧化氢被完全消耗后,这些小的活性物种就会聚合成具有混合多原子的Keggin型杂多阴离子,形成M-Ob—M（M=W或Mo）和M-Oc-M键．     

Synthesis, Crystal Structure, and Luminescent Property of One New Quinoxaline-substituted Nitronyl Nitroxide Complex [Ni（acac）2（NITQ）2].2CH2Cl2

A new complex, [Ni（acac）2（NITQ）2]-2CH2C12 1 （acac = acetylacetone, NITQ = 2-（2＂-quinoxalinyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide）, was synthesized and charac- terized by elemental analysis, IR spectroscopy, UV-Vis absorption spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 9.6970（19）, b = 20.410（4）, c = 12.166（2） A, β = 93.89（3）°, Mr = 997.43, V= 2402.3（8） A3, Z = 2, Dc = 1.379 g/cm3, F（000） = 1040,μ = 0.684 mm-1, the final R = 0.0423 and wR = 0.1197 for 2884 observed reflections （1 〉 2σ（I））. Compound 1 is found to assume a mononuclear structure, which is further linked into a three-dimensional （3D） supramolecular network by hydrogen-bonding, C1...O weak contact and π...π stacking interactions. Moreover, the luminescent properties of the ligand and compound 1 were further investigated in detail.     

碳前驱体CH3ArCH2NH2热解反应的热力学和动力学DFT研究

在实验研究基础上 ,通过量子化学理论计算对碳前驱体 CH3 Ar CH2 NH2 的热裂解机理作了进一步的研究 .利用 Gaussian98程序包中 AM1方法及 DFT UB3 LYP/3 -2 1 G*方法 ,对化合物 5种可能热裂解路径的热力学和动力学计算结果表明 ,CH3 Ar CH2 NH2 热裂解的主反应路径为生成自由基 CH3 Ar CH2 ·和 NH2 · ,其主反应路径 AM1计算的活化能 Ea=2 3 0 .78k J/mol,DFT计算的活化能 Ea=3 2 1 .1 8k J/mol;比较键焓计算的数据与相应的实验数据 ,发现 DFT计算结果与实验结果吻合得较好 ;通过分析优化的反应物及产物自由基的部分结构参数 ,了解了理论支持主反应的原因 ;计算的产物自由基的空间构型表明主反应路径生成的产物自由基相互间若进行稠环缩合反应 ,将获得分子平面取向性很好的稠环芳烃产物     

Synthesis and Crystal Structure of a Cr（Ⅲ） Dimer [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-Hydroxyoxyquinolate）

The title complex [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-hydroxyoxyquinolate） has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P^-1 with a = 8.719（1）, b = 9.226（1）, c = 9.717（1） A^°, α = 71.916（2）, β= 78.072（2）, γ = 76.014（2）°, V= 713.72（15） A^°^3, Z= 1, Dc= 1.597g/cm^3, F（000） = 350 and μ（MoKa） = 1.177 mm^-1, the final R = 0.0490 and wR = 0.1055 for 1616 observed reflections with I 〉 2σ（I）. It is a dimer constructed by two monomeric units [Cr（8-hqn）Cl2（H2O）] bridged by phenoxide-like oxygen atom from 8-hydroxyoxyquinolate, where the two six-coordinated Cr（Ⅲ）atoms exhibit an octahedral coordination geometry.     

NH2(～X2B1)与CH4反应机理的理论研究

在密度泛函理论B3LYP／6－311G^*水平下，研究了NH2与CH4的反应机理。通过振动频率和内禀反应坐标（IRC）分析，对反应过渡态进行了确认。在QCISD（T）／6－311G^*水平下进行了单点能计算，并进行了零点能校正，结果表明，反应NH2＋CH4→N3＋CH3是主要的反应通道。