配合物{[(C_9H_7)_3Yb]_2Cl}[Na·6THF](I)的合成及其还原生成(C_9H_7)_2Yb·2THF(II)的研究、配合物I和II的晶体结构

三氯化钇与茚基钠以 1∶2摩尔比于THF中 ,在 5 0℃下反应 ,歧化生成了离子型配合物 [(C9H7) 3 Yb] 2 Cl[Na·6THF](I) .X射线结构分析表明 ,配合物I是由阴离子 {[(C9H7) 3 Yb] 2 Cl}-及阳离子 [Na·6THF] 组成的离子对 ,阴离子由一个氯桥把两个 (C9H7) 3 Yb基团连接在一起 .配合物 [(C9H7) 3 Yb) 2 Cl] [Na·6THF]为三斜晶系 ,P1空间群 ,晶胞参数 ,a =1.0 682 (2 )nm ,b =1 2 687(3 )nm ,c=1 2 869(2 )nm ,α =87 2 2 3 (1)° ,β =81 75 5° ,γ =88 2 17° ,V =1 72 73 (1)nm3 ,Z =1.配合物I的结构用重原子法确定 ,用full matrixleast squares法修正 ,一致性因子为R =0 0 62 ,Rw =0 0 72 .配合物 {[(C9H7) 3 Yb] 2 Cl}[Na·6THF]与金属钠反应 ,生成 (C9H7) 2 Yb·2THF (II) .配合物II的分子结构经过了X射线的表证 .     

配合物{[(C9H7)3Yb]2Cl}[Na·6THF] (Ⅰ)的合成及其还原生成(C9H7)2Yb·2THF (Ⅱ)的研究、配合物I和II的晶体结构

三氯化钇与茚基钠以1∶2摩尔比于THF中,在50 ℃下反应,歧化生成了离子型配合物[(C9H7)3Yb]2Cl[Na·6THF] (Ⅰ). X射线结构分析表明,配合物Ⅰ是由阴离子{[(C9H7)3Yb]2Cl}-及阳离子[Na·6THF] 组成的离子对,阴离子由一个氯桥把两个(C9H7)3Yb基团连接在一起.配合物[(C9H7)3Yb)2Cl][Na·6THF]为三斜晶系,P1空间群,晶胞参数,a=1.0682(2) nm, b=1.2687(3) nm, c=1.2869(2) nm,α=87.223(1)°, β=81.755°, γ=88.217°, V=1.7273(1) nm3, Z=1.配合物I的结构用重原子法确定,用full-matrix least-squares法修正,一致性因子为 R=0.062, Rw=0.072.配合物{[(C9H7)3Yb]2Cl}[Na·6THF]与金属钠反应,生成(C9H7)2Yb·2THF (Ⅱ).配合物Ⅱ的分子结构经过了X射线的表证.     

新型Co(Ⅱ)配位聚合物的溶剂热合成与晶体结构

利用柔性含咪唑基配体1,3,5-三(咪唑-1-甲基)苯(L)与硫酸钴在溶剂热条件下反应,得到了一个配位聚合物{[Co(L)(EG)0.5(H2O)(SO4)]·EG·H2O}n(EG=乙二醇),并利用元素分析、红外光谱、X-射线单晶衍射等方法对其进行了表征。研究结果表明:此配合物属于三斜晶系,P1空间群,晶胞参数a=0.87430(9)nm,b=1.17042(13)nm,c=1.31161(14)nm,α=83.830(2)°,β=78.004(2)°,γ=73.938(2)°,V=1.2598(2)nm~3,Z=2。配合物中配体L连接Co(Ⅱ)形成一维链状结构,EG分子在配合物中连接链内的两个Co(Ⅱ)金属中心,硫酸根离子作为端基配体与Co(Ⅱ)配位。固态配合物中相邻的一维链通过分子间氢键O-H···O作用进一步构建为二维超分子结构。热重分析结果表明其配合物具有较好的热稳定。     

由芳香羧酸和1,3,5-三咪唑基苯为配体构筑的锌、镉配合物的合成、结构和荧光性质（英文）

通过水热法得到了2个配位聚合物{[Zn(timb)(BTEC)_(0.5)]·H_2O}n(1)和{[Cd(timb)(DPA)]·H_2O}n(2)(timb=1,3,5-三咪唑基苯,H4BTEC=均苯四甲酸,H2DPA=2,2-联苯二甲酸),对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。配合物1属于三斜晶系,P1空间群。配合物2属于单斜晶系,C2/c空间群。配合物1拥有一个不寻常的三维框架结构,其拓扑为(4.6~3·8~6)_2(4~2·8~4)(6~3)_2;而配合物2具有一维单层纳米管结构。结果说明了金属离子和有机羧酸配体在配合物组装过程中起着非常重要的作用。此外,在室温下对2个配合物进行了荧光性质分析。     

La（Ⅲ）、Nd（Ⅲ）与甜菜碱类衍生物形成的包含（H2O）6分子簇的配合物的晶体结构

利用配体1,5-二(3-羧基吡啶基)-N-甲基二乙胺(L)合成2种稀土金属配合物{[La2L4(H2O)2](ClO4)6·6H2O}n(1)和[Nd2L4(DMF)6(H2O)2]2(ClO4)6·4H2O(2)。用红外光谱和X-射线单晶衍射表征配合物的晶体结构。结构分析表明:配合物1属于三斜晶系,P1空间群,其晶胞参数为a=1.496 6(3)nm,b=1.559 7(4)nm,c=1.956 8(4)nm,α=86.776(6)°,β=77.723(7)°,γ=87.168(7)°,Z=2。在配合物1中,一对La髥原子被2个羧基桥联,形成双核结构;双核结构进一步被羧基连接,从而形成平行于c轴的一维链。值得注意的是配合物1的晶体结构中包含着由氢键连接的6个H2O分子组成的水分子簇。配合物2属于三斜晶系,P1空间群,晶胞参数为a=1.040 8(4)nm,b=1.354 1(5)nm,c=2.975(1)nm,α=94.390(8)°,β=91.720(7)°,γ=95.230(4)°,Z=2。配合物2中4个羧基连接一对Nd髥原子,形成四轮状结构,其中2个羧基采取syn-syn双原子桥联模式,而其余2个羧基则采取单原子桥联模式。     

具有穿插结构的金属钴配合物的合成、结构及电化学性质

在溶剂热体系中合成了3个中心金属为钴离子的具有穿插结构的金属有机配合物{[Co LB]·H_2O}_n(1),{[Co_2L_2(bimp)_(0.5)]·3H_2O}_n(2)和{[Co_2L_2B'_2]·2DMF}_n(3)[H_2L=4,4'-三苯胺二甲酸;B=1,3-二(咪唑基)苯,bimp=3,5-二(1-咪唑)吡啶,B'=1,4-双(咪唑基)苯].通过单晶及粉末X射线衍射和热重分析对这3个配合物进行了表征.结果表明,配合物1~3均结晶于单斜晶系,其中配合物1属C2/c空间群,配合物2属P2/n空间群,配合物3属P2_1空间群;在配合物1和3中Co~(2+)为四配位模式,而在配合物2中Co~(2+)为五配位,并以双核桨轮形的结构单元[Co_2(CO_2)_4]存在;配合物1和2均为二重穿插结构的三维超分子网络,配合物3是一个四重穿插的三维超分子网络.电化学性质研究结果表明,配合物1~3是电化学活性物质,电化学可逆性较好.     

La(Ⅲ)、Nd(Ⅲ)与甜菜碱类衍生物形成的包含(H_2O)_6分子簇的配合物的晶体结构（英文）

利用配体1,5-二(3-羧基吡啶基)-N-甲基二乙胺(L)合成2种稀土金属配合物{[La2L4(H2O)2](ClO4)6·6H2O}n(1)和[Nd2L4(DMF)6(H2O)2]2(ClO4)6·4H2O(2)。用红外光谱和X-射线单晶衍射表征配合物的晶体结构。结构分析表明:配合物1属于三斜晶系,P1空间群,其晶胞参数为a=1.496 6(3)nm,b=1.559 7(4)nm,c=1.956 8(4)nm,α=86.776(6)°,β=77.723(7)°,γ=87.168(7)°,Z=2。在配合物1中,一对La髥原子被2个羧基桥联,形成双核结构;双核结构进一步被羧基连接,从而形成平行于c轴的一维链。值得注意的是配合物1的晶体结构中包含着由氢键连接的6个H2O分子组成的水分子簇。配合物2属于三斜晶系,P1空间群,晶胞参数为a=1.040 8(4)nm,b=1.354 1(5)nm,c=2.975(1)nm,α=94.390(8)°,β=91.720(7)°,γ=95.230(4)°,Z=2。配合物2中4个羧基连接一对Nd髥原子,形成四轮状结构,其中2个羧基采取syn-syn双原子桥联模式,而其余2个羧基则采取单原子桥联模式。     

二烷基二硫代氨基甲酸砷(Ⅲ)、铋(Ⅲ)配合物的合成、晶体结构及抑菌活性

合成了二丁基二硫代氨基甲酸砷[(C9H18NS2)3As(Ⅲ)](1)和二甲基二硫代氨基甲酸铋[(C3H6NS2)3Bi(Ⅲ)](2)两种配合物。通过元素分析、红外光谱、1H NMR、热重对其进行表征,并用X-射线单晶衍射测定了晶体结构。配合物1属于三斜晶系,P 1-空间群,晶胞参数为:a=1.075 0(15)nm,b=1.2143(16)nm,c=1.621(3)nm,α=69.15(2)°,β=75.36(3)°,γ=88.17(2)°,Z=2,V=1.910(5)nm3,Dc=1.197 g.cm-3;配合物2也属于三斜晶系,P 1-空间群,晶胞参数为:a=0.992 9(3)nm,b=0.993 0(3)nm,c=1.142 7(3)nm,α=64.495(4)°,β=80.400(4)°,γ=64.772(4)°,Z=2,V=0.914 7(4)nm3,Dc=2.068 g.cm-3。配合物1中的As(Ⅲ)与来自3个配体中的6个硫原子配位,形成6配位畸变八面体构型;配合物2则形成6配位畸变五角锥构型,其分子之间又通过Bi···S弱相互作用构成二聚体结构。利用琼脂扩散法测试了配合物的抑菌活性,结果表明配合物1对5种受试菌株具有较强的抑菌活性,配合物2则仅有弱的抑菌性。     

新型配位聚合物[Zn6（bta）4（2,2′-bipy）3]的合成、晶体结构和荧光性质

采用水热法合成了一种新的三维配位聚合物[Zn6(bta)4(2,2′-bipy)3](H3bta=1,3,5-苯三乙酸;2,2′-bipy=2,2′-二联吡啶),并通过X射线单晶结构分析、红外光谱、元素分析和热重分析对该配合物进行了表征.结构分析数据表明,该配合物属单斜晶系,Cc空间群,晶胞参数a=1·7714(4)nm,b=2·4391(5)nm,c=1·7120(3)nm,β=104·39(3)°,Z=4,V=7·165(2)nm3,Dc=1·722g/cm3,μ=2·065mm-1,F(000)=3768,R1=0·0645,wR2=0·1424.荧光光谱结果表明,配合物具有良好的荧光性质.     

草酸根桥联双核配合物[Cd2(phen)2ox(NO3)2·(H2O)2]的合成、结构及态密度分析

通过草酸钾(k2ox·H2O)、硝酸镉[Cd(NO3)2·4H2O]和1,10-邻菲咯啉(phen)在甲醇·水溶液中的反应合成了一种双核镉配合物[Cd2(phen)2ox(NO3)2(H2O)2],其结构经单晶X射线衍射表征.配合物属三斜晶系,P(1)空间群,晶胞参数:a=0.67629(14)nm,b=1.0051(2)nm,c=1.0527(2)nm,α=109.19(3)°,β=92.12(3)°,γ=93.48(3)°,γ=0.6733(2)nm3,Z=1,D=2.055 g/cm3,F(000)=410,μ=1.660mm-1,R=0.0445,wR=0.0877.配合物为草酸根桥联的双核镉配合物,且草酸根C-C键中点为配合物的倒反中心,镉与ox2-,phen,NO3-和水配位.运用晶体场理论计算了其态密度,结果表明NO3-和phen对配合物的性质有重要影响.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.