聚苯醚砜在二甲基甲酰胺中稀溶液性质的研究(Ⅱ)

本文用广角及准弹性光散射法测定了聚苯醚砜各级分在DMF中和在θ溶剂中25℃时的均才半径R_G,第二维利系数A_2,流体力学半经R_H,扩散系数D_O,扩散系数的浓度依赖性k_F以及这些参数与分子量M的关系。它们的结果如下R_G=0.031MO~(0.55) D_O(θ)=0.906×10~(-4)M~(0.5) D_0=1.445×10~(-4)M~(0.55)A_2=0.033M~(-0.35) k_D(θ)=0.5M~(0.34) k_D=2.3×10~(-6)M~(1.36)α_H=R_H/R_H(θ)=0.63M~(0.05)R_H(θ)=0.0299M~(0.5)R_H=0.0188M~(0.55) 作者讨论了静态与动态两种高分子尺寸之间的关系;三种溶胀因子α_η和、α_H、α_G之间的关系;以及摩擦系数的浓度系数k_F与流体力学体积V_H之间的关系。它们的结果满足下面各关系式: R_H/R_G=[π(v+1)(2v+1)/3]~(1/2)(2-v)(1-v)/2, α_η~3=α_(G)~2α_H, k_F=1.2A_2M+N_AV_H/M,K_F(θ)=N_AV_H/M     

硫在疏质子介质中电化学还原机理的研究 Ⅰ.第一步氧化还原过程的研究

本文用电化学方法研究了硫在 DMSO 溶剂中第一步氧化还原过程的机理,发现这个过程不是一个简单的双电子过程,提出了更为合理的 EEC 机理,数字模拟也表明该机理是可能的,并从2.5次微分谱上发现了 S_6~(2-)的氧化峰,其峰电位为-0.29V(相对于银电极).计算得该体系的某些动力学参数值为:α_1=0.5,β_2=0.25,K°_(f1)=8.2×10~(-5)cm·s~(-1),k°_(b2)=3.5×10~(-5)cm·s~(-1)(电位零点-0.851V)D_(s_8)=5.6×10~(-6)cm~2·s~(-1),D_(s_6~(2-))=8.4×10~(-6)cm~2·s~(-1).     

二苄亚砜硝酸钕的晶体结构

二苄亚砜硝酸钕Nd(NO_3)_3·[(C_6H_5CH_2)_2S0]属三斜晶系,P1空间群,晶胞参数:a=9.835(2),b=12.445(2),c=19.971(5)A,α=104.13(2)°,β=90.34(2)°γ=74.96(1)°Z=2。晶体结构用重原子法解出,经最小二乘修正后R因子为0.031。钕离子由九个氧配位,形成稍歪扭的三帽三方棱柱配位多面体,其中一个三角面由三个二苄亚砜(DBSO)提供的氧形成,其他氧原子则由硝酸根提供。平均Nd-O(DBSO)=2.379A,Nd-O(NO_3)=2.536A。     

Crystal and Molecular Structure of Ethyl 2-[（4-Hydroxy-phenyl）hydrazono]-3-oxobutanoate

The title compound,C 12 N 2 O 4 H 14 (M r=250.3),crystallizes in triclinic P1 space group with a=7.7709(9),b=8.7534(11),c=9.6958(12),α=77.103(2),β=80.496(2),γ=86.726(2)o,V=633.9(1) 3,Z=2,F(000)=264,D c=1.311 Mg/m 3,μ(MoKα)=0.1 mm-1,the final R=0.056,and wR=0.15 for 2239 observed reflections (I > 2σ(Ⅰ)).The molecules in the crystal are linked through O-H···O type of hydrogen bonding interaction forming an infinite chainlike structure.The phenylhydrazone ring and oxobutanoate groups are almost planar.The keto hydrazo group adopts a Z-configuration in the molecule and the torsion angle is-177.6(2)°.     

Na_3H_2[PMo_(10)V_2O_(40)]·16H_2O的合成与晶体结构

标题化合物的晶体属P2_1/m空间群,α=13.821(2),b=15.355(3),c=11.597(2),β=107.50(2)°,V=2347.2~3,M_r=2091.46,Z=2,D_c=2.959 g·cm~(-3),μ(MoK_o)=30.77cm~(-1),F(000)=1992。用4049个独立可观测衍射精修结构,R=0.033。杂多酸阴离子[PMo_(10)V_2O_(40)]~(5-)具有准Keggin结构,12个金属原子呈无序分布,中心原子P与两个齿顶原子M(Mo/V)在对称面上。P—O平均键长1.541(2),M—O键长1.671(2)-2.432(2)。除一个Na—O配位多面体为畸变三方锥外,其余四个Na—O配位体均为六配位。讨论了Na~+离子呈无序分布的晶体结构特征并初步总结[PMo_(10)V_2O_(40)]~(5-)在不同晶相中的构型。     

硫氰酸铈(Ⅲ)与三缩四乙二醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_2O)]的合成及晶体结构

合成了硫氰酸铈(Ⅲ)与三缩四乙醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_(2)O)].晶体结构分析表明,该配合物晶体属三斜晶系,P(?)空间群.晶胞参数:a=0.8816(3)nm,b=1.0465(2)nm,c=1.2490(2)nm,α=86.46(1)°,β=70.90(2)°,γ=66.37(2)°,ν=0.9943nm~(3),Z=2.D_(计算)=1.769cm~(3),最终偏差因子R=0.049.     

STRUCTURE OF TRANS-SYN-BIS-[(η-(CH_3)_2CHC_5H_4)Mo (μ-S)(μ-SC(CH_3)_3)]

<正> Mr = 648.75, triclinic, space group P1 , a = 10.087(4), b = 12.686(5), c = 14.222(6) A, α= 104.83(3)°, β = 124.61(4)°, γ = 90.98(3)°, V = 1417.22A3, Z = 2, De = 1.520 Mg.m-3, (MoKα)= 0.71069A, μ(MoKα) = 11.597 cm-1, F(000) = 664, room temperature. Final R=0.0424 for 5705 observed reflections. In the molecule two metal atoms are bonded togetherin a cavity surrounded by Ugands. Pour sulphur atoms are in bridging positions and in the same plane perpendicular to the metal-metal vector with the two t-butylthiolato ligands being in mutu-syn positions.     

STRUCTURE OF 5-(N-METHYL-β-NAPHTHYLAMINO)-PENTA-2,4-DIENAL,C_(16)H_(15)NO

<正> M=237.31, orthorhombic, Pbca, a=8.342(2), b=15.675(3), c=19.779 (4)A3, Z=8, Dx=1.21 g/cm3, λ(MoKα)=0.71069A, μ=0.71 cm-1, F(000)=1008, room temperture, R=0.046. The planes of the formyl butadienyl group and the naph-thyl ring are tilted with respect to the plane of the nitrogen frame N by 2.8° and 31.4° , respectively. The O atom and the methyl group are in Z position.     

THE STRUCTURE OF N-METHYL-CINNOLINE TCNQ_2 II.THE STRUCTURE OF IN-METHYL-CINNOLINE TCNQ_2

<正> M =553.6, triclinic,Pl, a=6.5157(22), b=7.7153(14), c=13.9146(28)A; α=88.394(16)°, β=84.288(22)°, γ=78.749(22)°, V=682.62(30)A3, Z=1; μ(MoKα)= 0.80cm-1, F(000)=284.92, room temperature. The final R=0.0537 for 1230 independent reflections. Planar tetracyanoquinodimethane(TCNQ). stacks along a axis with the molecular planes parallel to each other. The separations between TCNQs are 3.2698 and 3.2448. The overlaps of TCNQs are of the ring-external bond type. This mode of TCNQ stacking is used to explain the conductivity of the title compound. The D.C. conductivity along needle axis is σ(RT)=10(Ωcm)-1 1.     

Synthesis and structure of an open-type trinuclear molybdenum cluster compound[Mo_3(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2]·0.5CH_2Cl_2·2H_2O

The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.