4-(2'-羟基苯甲酰肼)苯亚甲基／亚乙基－5－甲基－2－苯基－2，4－二氢－吡唑啉酮－3超分子化合物的合成与晶体结构

报道了4-(2'－羟基苯甲酰肼)苯亚甲基－5－甲基－2－苯基－2，4－二氢－吡 唑啉酮－3（B_1）和4-(2'－羟基苯甲酰肼)亚乙基－5－甲基－2－苯基－2，4－二 氢－吡唑啉酮－3（B_2）的合成、表征及晶体结构分析，B_1晶体属单斜晶系， C2/c空间群，所得晶胞参数为：a = 1.4201(2) nm, b = 1.65542(2) nm, c = 1. 8455(3) nm, β = 101.32(1)°，V = 4.2541(10) nm~3, Z = 8, D_c = 1.344 g/cm~3, μ = 0.094 mm~(-1), F(000) = 1808, R = 0.0442, wR = 0.1037。该 化合物由水分子通过氢键连接成沿ac面无限延伸的二维网络结构的超分子。B_2晶 体属三斜晶系，P1空间群，a = 1.2120(2) nm, b = 1.2223 (2) nm, c = 1.4159 (3) nm, α = 70.38 (1)°, β = 74.91 (1)°, γ = 63.64(1)°, V = 1.7549 (5)° nm~3, Z = 4, D_c = 1.326 g/cm~3, μ = 0.092 mm~(-1), F(000) = 736, R = 0.0436, wR = 0.1076。此化合物通过分子间氢键形成沿α轴无限延伸的一维 链状结构的超分子，由于分子间的作用力使其分子又沿b轴呈层状堆积。     

1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。     

1,1,1-三[3-（2-苯并咪唑基）-2-氧杂丙基]丙烷镍配合物合成以及结构测定

合成了一个新的三脚架结构配体及其镍配合物的晶体。该晶体属单斜晶系， P2_l/n空间群，a = 1.2151(4) nm, b = 1.5535(5) nm, c = 2.1740(7) nm, β = 90.551(18)°, V = 4.103(2) nm~3, Z = 4, M_r = 834.03, R = 0.0556, wR = 0.1256, μ = 0.541 mm~(-1), F(000) = 1758。配合物中Ni与配体的三个N和 三个O构成六配位变形八面体结构。晶体中存在着分子间氢键，晶体结构依靠库仑 力和氢键作用而稳定。     

4-(2′-羟基苯甲酰肼)苯亚甲基/亚乙基-5-甲基-2-苯基-2,4-二氢-吡唑啉酮-3超分子化合物的合成与晶体结构

报道了 4 (2′ 羟基苯甲酰肼 )苯亚甲基 5 甲基 2 苯基 2 ,4 二氢 -吡唑啉酮 3 (B1)和 4 (2′ 羟基苯甲酰肼 )亚乙基 5 甲基 2 苯基 2 ,4 二氢 -吡唑啉酮 3 (B2 )的合成、表征及晶体结构分析 ,B1晶体属单斜晶系 ,C2 /c空间群 ,所得晶胞参数为 :a =1.42 0 1(2 )nm ,b =1.65 5 42 (2 )nm ,c =1.845 5 (3 )nm ,β =10 1.3 2 (1)° ,V =4.2 5 41(10 )nm3 ,Z =8,Dc=1.3 44g/cm3 ,μ =0 .0 94mm-1,F(0 0 0 ) =180 8,R =0 .0 44 2 ,wR =0 .10 3 7.该化合物由水分子通过氢键连接成沿ac面无限延伸的二维网络结构的超分子 .B2 晶体属三斜晶系 ,P 1空间群 ,a =1.2 12 0 (2 )nm ,b =1.2 2 2 3 (2 )nm ,c =1.415 9(3 )nm ,α =70 .3 8(1)° ,β =74.91(1)° ,γ =63 .64 (1)° ,V =1.75 49(5 )nm3 ,Z =4,Dc=1.3 2 6g/cm3 ,μ =0 .0 92mm-1,F(0 0 0 ) =73 6,R =0 0 43 6,wR =0 .10 76.此化合物通过分子间氢键形成沿a轴无限延伸的一维链状结构的超分子 ,由于分子间的作用力使其分子又沿b轴呈层状堆积     

二维无机－有机杂化层网骨架晶体的合成与结构

在温和条件下合成了二维层网结构的无机－有机杂化晶体Zn(BDC)(C_3H_3N_2) ·(DMF)(1)和Co_2(BDC)_2(C_5H_5N)_4·2(DMF)·(C_5H_5N)·(C_5H_5N) (2)，并 通过ICP和X射线单晶衍射分析等手段对其结构进行了表征。1的晶胞数据：C_(14) H_(14)N_3O_5Zn, M_r = 369.65，单斜晶系，C2/c空间群，晶胞参数a = 2.1059 (4) nm, c = 1.4836(3) nm, β = 99.09(3)°，V = 3.1826(11) nm~3, Z = 4, D_X = 1.543 Mg/m~3, μ = 1.571 mm~(-1), F(000) = 1512。最后的一致性因子 为R = 0.0697, R_w = 0.2018。2的晶胞数据：C_(47)H_(47)N_7O_(10)Co_2, M_r = 987.78，单斜晶系，P2(1)/n空间群，晶胞参数a = 1.0829(2) nm, b = 1. 5431(3) nm, c = 1.4428(3) nm, β = 101.65(3)°，V = 2.3612(8) nm~3, Z = 2, D_X = 1.391 Mg/m~3, μ = 0.767 mm~(-1), F(000) = 1024。最后的一致性 因子为R = nm, β = 101.65(3)°, V = 2.3612(8) nm~3, Z = 2, D_X = 1.391 Mg/m~3, μ = 0.767 mm~(-1), F(000) = 1024。最后的一致性因子为R = 0. 0652，R_w = 0.1888。1和2的结构都是由无机簇M_2(CO_2)_4(M = Zn, Co)通过苯 环连接而形成的层网结构。它们都存在由4个无机簇与4个苯环形成的环，其大小约 为0.9 nm * 0.9 nm。由于咪唑和吡啶分别与1和2无机簇的两极配位，阻止了它们 形成三维骨架结构。     

有机锡氧羧酸簇合物[PhCH_2Sn(O)(O_2CCH=CHAr)]_6的合成、表征和[PhCH_2Sn(O)(O_2CCH=CHPh)]_6的晶体结构

利用(PhCH_2)_3Sn]_2O与ArCH=CHCO_2H反应，合成6个新的[PhCH_2Sn(O) (O_2CCH=CHAr)]_6簇合物。通过元素分析、红外光谱和X射线单晶衍射对其结构进 行了表征。用X射线单晶衍射测定了[PhCH_2Sn(O)(O_2CCH=CHPh)]_6的晶体结构， 结果表明，该簇合物为三斜晶系，空间群P1, a = 1.6771(3) nm, b = 1.8020(4) nm, c = 2.1073(4) nm, α = 108.111(3)°β = 103.614(3)°,γ = 104.679 (3)°,Z = 2, V = 5.5033(18) nm~3, D_c = 1.350 g/cm~3, μ = 1.396 mm~(-1) , F(000) = 2208, R = 0.0606, wR = 0.698。该化合物为鼓型簇状结构，锡原子 呈畸变的八面体构型。     

含N-苯甲酰皮考林酰肼的钒酰、镍及锰配合物的合成和晶体结构

合成了3个含N-苯甲酰皮考林酰肼(简写为HL)的钒、镍和锰配合物[VO_2L](1,C_(13)H_(10)N_3O_4V,M_r=323.18),[NiL_2]·0.5CH_3OH(2,C_(26.5)H_(22)N_6NiO_(4.5),Mr=555.21)和[MnL_2]·0.5CH_3OH(3,C_(26.5)H_(22)MnN_6O_(4.5),Mr=551.44)。配合物1属三斜晶系,空间群为P1,a=0.71241(3)nm,b=0.89625(6)nm,c=1.11706(6)nm,α=94.715(2)°,β=102.053(2)°,γ=112.375(3)°,V=0.63461(7)nm~3,Z=2,F(000)=328,μ(MoKα)=0.802mm~(-1),R=0.0290,wR=0.0816;配合物2属单斜晶系,空间群为C2/c,a=2.5875(1)nm,b=1.4868(1)nm,c=1.8353(1)nm,β=134.470(4)°,V=5.2081(5)nm~3,Z=8,F(000)=2368,μ(MoKα)=0.795mm~(-1),R=0.0459,wR=0.1330;配合物3属单斜晶系,空间群为C2/c,a=2.60113(3)nm,b=1.45231(4)nm,c=1.92903(1)nm,β=132.824(1)°,V=5.3448(2)nm~3,Z=8,F(000)=2344,μ(MoKα)=0.543mm~(-1),R=0.0457,wR=0.1325。在配合物1中,钒(V)原子具有畸变的N_2O_3四角锥配位构型,晶体内每两个分子通过分子间氢键作用形成缔合分子对。在配合物2和配合物3中,镍(Ⅱ)原子和锰(Ⅱ)原子具有扭曲的N_4O_2八面体配位构型,晶体通过分子间氢键作用形成一维的无限链状结构。红外光谱表明,配体在形成配合物后,ν(C=O)和ν(C=N)红移。电     

双核有机锡（IV）配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)-SnPh_3]·2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH的合成、表征和晶体结构

利用三苯基氯化锡和对苯二甲酸二钠、哌嗪荒酸二钠在甲醇中反应，合成了双 核有机锡（IV）配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)SnPh_3]· 2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH（2）。通过元素分 析、红外光谱和核磁共振氢谱对其结构进行了表征。用X射线单晶衍测定了这两个 化合物的晶体结构。化合物质1为单斜晶系，空间群P2_1/n，a = 1.5199(5) nm， b = 0.9000(3) nm，c = 1.8206(6) nm，β=113.970(5)°，Z = 2，V = 2.2755 (13) nm~3，D_c = 1.413 g/cm~3，μ = 1.146 mm~(-1)，F(000) = 980，R_1 = 0.0353，wR_2 = 0.0606。化合物2为单斜晶系，空间群P2_1/c，a = 1.5066(5) nm，b = 1.0875(4) nm，c = 1.3542(5) nm，β=91.614(5)°，Z = 2，V = 2. 2178(14) nm~3，D_c = 1.498 g/cm~3，μ=1.351 mm~(-1)，F(000) = 1008，R_1 = 0.0401，wR_2 = 0.1148。在1和2的晶体中，锡原子呈五配位畸变三角双锥构型 。配合物1由未配位的甲醇分子通过氢键作用形成二维网状结构。     

双核有机锡（IV）配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)-SnPh_3]·2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH的合成、表征和晶体结构

利用三苯基氯化锡和对苯二甲酸二钠、哌嗪荒酸二钠在甲醇中反应，合成了双 核有机锡（IV）配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)SnPh_3]· 2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH（2）。通过元素分 析、红外光谱和核磁共振氢谱对其结构进行了表征。用X射线单晶衍测定了这两个 化合物的晶体结构。化合物质1为单斜晶系，空间群P2_1/n，a = 1.5199(5) nm， b = 0.9000(3) nm，c = 1.8206(6) nm，β=113.970(5)°，Z = 2，V = 2.2755 (13) nm~3，D_c = 1.413 g/cm~3，μ = 1.146 mm~(-1)，F(000) = 980，R_1 = 0.0353，wR_2 = 0.0606。化合物2为单斜晶系，空间群P2_1/c，a = 1.5066(5) nm，b = 1.0875(4) nm，c = 1.3542(5) nm，β=91.614(5)°，Z = 2，V = 2. 2178(14) nm~3，D_c = 1.498 g/cm~3，μ=1.351 mm~(-1)，F(000) = 1008，R_1 = 0.0401，wR_2 = 0.1148。在1和2的晶体中，锡原子呈五配位畸变三角双锥构型 。配合物1由未配位的甲醇分子通过氢键作用形成二维网状结构。     

1，3，5－三咪唑基苯－醋酸锌配合物的合成、结构和离子交换性质研究

报道了一个由新型三角架配体1,3,5-三咪唑基苯（L）与Zn(CH_3COO)_2· 2h_2O组装得到的配合物：[Zn(L)_2(H_2O)_2]-(CH_3COO)_2·2H_2O (1)，用X射线 单晶衍射法测定了配合物的晶体结构，该晶体属单斜晶系，空间群P2_1/n，晶胞参 数a = 0.8339(1) nm, b = 1.2209(2) nm, c = 1.7565(3) nm, β = 94.880(3)° ，D_c = 1.383 g/cm~3, μ = 1.505 mm~(-1), F(000) = 1560, R_1 = 0.0429, wR_2 = 0.0713。配合物1具有二维层状结构，醋酸根阴离子位于层与层之间的孔 道中，并且可以被硝酸根离子交换。     

Syntheses of 2-hydroperoxy-and 2-hydroxy-2H-imidazoles

Oxidation of fully substituted imidazoles 1 by singlet oxygen gives in good yield fully substituted 2-hydroperoxy-2H-imidazoles 2 . Reduction of 2 by triphenylphosphine leads to 2-hydroxy-2H-irnidazoles 3 . Limitations of the methods are reported.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Efficient C2 functionalisation of 2H-2-imidazolines

Alkylation and oxidation of 2H-2-imidazolines, followed by regioselective deprotection, thionation and microwave-assisted Liebeskind-Srogl reaction, efficiently led to 2-aryl-2-imidazolines as new analogues of p53-hdm2 interaction inhibitors (Nutlins).     

Homopolymerization of 2-alkyl- and 2-aryl-2-oxazolines

2-Aryl- and 2-alkyl-2-oxazolines have been polymerized to poly-(N-aroyl)aziridines and poly(N-acyl)aziridines, respectively, in the presence of boron trifluoride. The polymers obtained were glassy, light yellow resins with molecular weights ranging from 3500 to 7500 (35–50 oxazoline units per chain). The polymerization rates have been determined for several of these monomers. A polymerization mechanism is proposed.     

Stereoselective synthesis of 2-deoxy-beta-galactosides via 2-deoxy-2-bromo- and 2-deoxy-2-iodo-galactopyranosyl donors

[reaction: see text] A series of 2-bromo- and 2-iodo-galactopyranosyl acetates and trichloroacetimidates were evaluated as glycosyl donors for the synthesis of 2-deoxygalactopyranosides. The best selectivity for the beta-glycosidic linkage was achieved by using 6-deoxy-3,4-carbonate-protected galactosyl donors.