具有不同类型桥基的双核Cu(Ⅱ)-Schiff碱配合物的合成和晶体结构

合成了３个分别以Ｃ２Ｏ２－４（［Ｃｕ２（Ｌ１）２（ｏｘ）］，１），ＡｃＯ－（［Ｃｕ２（ＡｃＯ）（Ｌ２）２］ＢＦ４，２）和酚氧（［Ｃｕ２（Ｌ３）２］（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物［Ｃｕ２（Ｌ１）２（ｏｘ）］·［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ（１′）及２和３的晶体结构．Ｘ射线衍射结果表明：１′，２和３分别属于Ｆｄｄｄ，Ｐ２１／ｃ和Ｐ２１／ｃ空间群．晶胞参数：［Ｃｕ２（Ｌ１）２（ｏｘ）］［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ，ａ＝２．４３９０（４）ｎｍ，ｂ＝３．０５３８（６）ｎｍ，ｃ＝１．８４９４（６）ｎｍ，α＝β＝γ＝９０．００°；２，ａ＝０．８４７（１）ｎｍ，ｂ＝２．６５４２（８）ｎｍ，ｃ＝１．４１００（６）ｎｍ，β＝９１．３４（６）°；３，ａ＝０．７６４６（３）ｎｍ，ｂ＝１．６９８３（３）ｎｍ，ｃ＝２．４４１７（３）ｎｍ，β＝９７．１１°     

μ－4，4＇－联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４＇－联吡啶为桥联配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·２Ｈ＿２Ｏ（１）、［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３］（ｂｐｙ）＿３］（ＣｌＯ＿４）＿６·Ｈ＿２Ｏ（２）和［Ｃｕ＿３（４，４＇－ｂｐｙ）＿３·（ＮＯ＿２－ｐｈｅｎ）＿３］（ＣｌＯ＿４）＿６·６Ｈ＿２Ｏ（３）。经元素分析、电导、ＩＲ、电子光谱、ＥＳＲ、磁化率等方法进行了表征，推定该配合物具有以４，４＇－联吡啶为扩展桥的结构。利用Ｈｅｉｓｅｎｂｅｒｇ模型求得交换参数Ｊ值为－０．２３ｃｍ－１（１）和－０．９０ｃｍ－１（３），表明配合物中金属离子间仅有很弱的反铁磁交换作用．     

邻菲罗啉-氨基酸铜(Ⅱ)配合物的合成及表征

合成了三种邻菲罗啉（Ｐｈｅｎ）－氨基酸酮（Ⅱ）的配合物：［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｈｉｓ）］·２ＣｌＯ４·Ｈ２Ｏ,［Ｃｕ（Ｐｈｅｎ）（Ｇｌｙ）］·ＣｌＯ４·Ｈ２Ｏ和［Ｃｕ（Ｐｈｅｎ）（Ｌ－Ｐｒｏ）］·ＣｌＯ４·０．５Ｃ２Ｈ５ＯＨ（Ｌ－Ｈｉｓ：组氨酸;Ｇｌｙ：甘氨酸：Ｌ－Ｐｒｏ：脯氨酸）。用元素分析、摩尔电导、ＩＲ和电子吸收光谱等手段对配合物进行了表征     

［Ln（HCOO）_3·phen·C_2H_5OH］［Ln＝Pr、Gd］的电子

［Ｌｎ（ＨＣＯＯ）＿３·ｐｈｅｎ·Ｃ＿２Ｈ＿５ＯＨ］［Ｌｎ＝Ｐｒ、Ｇｄ］的电子结构和化学键董南，朱龙观，蔡国强，吴念慈（杭州大学化学系杭州３１００２８）关键词：化学键，电子结构，ＩＮＤＯ，配合物［Ｌｎ（ＣＣｌ＿３ＣＯＯ）＿３·ｐｈｅｎ·Ｃ＿２Ｈ＿５Ｏ...     

二硫代草酰胺基或二环己酮草酰二腙作桥联基的新型双核Cu（Ⅱ）－Cu（Ⅱ）配合物的合成和磁性（Ⅱ）

合成和表征了四种新的以二硫代草酰胺基（ｄｔＯ２－）或二环己酮草酰二腙（ＢＣＯ）作桥基的双核金属配合物［Ｃｕ２（ｐｈｅｎ）２（ｄｔＯ）］（ＣｌＯ４）２（１）、［Ｃｕ２（ｄｉｅｎ）２（ｄｔＯ）］（ＣｌＯ４）２·２Ｈ２Ｏ（２）、［Ｎｉ２（ｄｉｅｎ）２（Ｈ２Ｏ）２（ｄｔＯ）］（ＣｌＯ４）２（３）及［Ｃｕ２（ｐｈｅｎ）２（ＣｌＯ４）２（ＢＣＯ）］（ＣｌＯ４）２（４），（ｐｈｅｎ：１，１０－邻菲咯啉，ｄｉｅｎ：二乙烯三胺）。测定了配合物１和４的变温磁化率，并求出交换积分Ｊ分别为－７．６７（１）和－０．９２（４）ｃｍ－１，表明双核配合物中铜离子间存在反铁磁性自旋交换相互作用。     

铜与三乙四胺六乙酸配合物［Cu_2（H_2TTHA）（H_2O）_2］·6H_2

首次在水溶液中合成了三乙四胺六乙酸铜配合物单晶，元素分析结果表明可用Ｃｕ２（Ｈ２ＴＴＨＡ）·８Ｈ２Ｏ表示．用Ｘ射线衍射方法测定了该单晶结构，其结构式为［Ｃｕ２（Ｈ２ＴＴＨＡ）（Ｈ２Ｏ）２］·６Ｈ２Ｏ．晶体属单斜晶系．空间群为，每一晶胞中有２个配合物单元，形成二核配合物．晶胞参数如下：ａ＝０．７１６２（４），ｂ＝１．３０７７（８），ｃ＝１．５８３９（９）ｎｍ；β＝９１．６６（５）°，Ｚ＝２，ｖ＝１．４８３（２）ｎｍ３，ｄｃａｌｃ＝１．７０６ｇ／ｃｍ３．配合物铜的配位数为５，构型为四方锥配位多面体．     

Yb(Cl_4)_3·3H_2O-18C6-C_2H_5OH体系(25℃)的相化学研究及固态配合物的合成与性质

王冠醚能选择性配位于阳离子,使无机盐溶于有机溶剂及类似酶功能的特性,因而引起人们很大的研究兴趣。文献［１］报道在乙腈中制得了组成为：Ｃｅ（ＣＩＯ４）３·１８Ｃ６的配合物;文献［２］在乙腈中制得了组成为 ＲＥ（ＣＩＯ４） ３· １８Ｃ６（ＲＥ＝ Ｐｒ, Ｅｕｆ）的配合物;而 ＲＥ（ＣＩＯ４） ３·３Ｈ２Ｏ－１８Ｃ６－ＣＨ３ＣＮ体系（ＲＥ＝ Ｄｙ, Ｙ）的相化学研究指出：体系中均形成两种化学计量的配合物［３·４］。Ｙｂ（ＣＩＯ４）３·３Ｈ２Ｏ与１８Ｃ６在乙醇中的配合行为未见报道。为了寻找制备配合物的热力学依…     

2,6—二甲酸吡啶氮氧化物与稀土硝酸盐配合物的合成及表征

在无水乙醇介质中合成了２，６－二甲酸吡啶氮氧化物（Ｈ２ＰｄＣＯ）和稀土硝酸盐形成的配合物［ＲＥ（ＰｄＣＯ）·ＮＯ３·２Ｈ２Ｏ］（ＲＥ＝Ｌａ－Ｎａ，Ｓｍ，Ｅｕ，Ｔｂ，Ｈｏ，Ｅｒ，Ｙ）。通过元素分析，摩尔电导，红外光谱，紫外光谱，１Ｈ核磁共振谱及热重－差热分析等对该系列配合物进行了表征，并研究了Ｅｕ（Ⅲ），Ｔｂ（Ⅲ）配合物荧光性质。     

［Cu_2（Gly－GlyO）_2（4，4＇－bpy）（OH）_2］·9H_2O

将Ｇｌｙ－ＧｌｙＯ、４，４＇－联吡啶与Ｃｕ（ＮＯ_３）_２·Ｈ_２Ｏ在二次水溶液中反应，合成出以４，４＇－ｂｐｙ为中继基、Ｃｌｙ－ＧｌｙＯ为螯环的新型双核铜配合物，经Ｘ射线单晶结构分析确定该配合物晶体的化学结构式为［（Ｈ_２ＮＣＨ_２ＣＯＮＨＣＨ_２ＣＯＯ）Ｃｕ（ＯＨ）（Ｃ_（１０）Ｈ_８Ｎ_２）Ｃｕ（ＯＮ）（Ｈ_２ＮＣＨ_２ＣＯＮＨＣＨ_２ＣＯＯ）］·９Ｈ_２Ｏ．晶体属Ｐ　空间群，晶胞参数ａ＝１．１４１２ｎｍ，ｂ＝１．２２９８ｎｍ，ｃ＝１．４２６９ｎｍ，α＝１１３．８２°，β＝１０１．９１°，γ＝１０３．６４°，Ｚ＝２．最终一致性因子Ｒ值为０．０６８，Ｒ_ｗ值为０．０５７，标准偏差σ＝０．１９５１。     

μ—4,4‘—联吡啶桥联三核Cu（Ⅱ）配合物的合成和磁性

合成了３种以４，４’－联吡啶为配体的三核环状Ｃｕ（Ⅱ）配合物［Ｃｕ３（４，４＇－ｂｐｙ）３．（ｐｈｅｎ）３］（ＣｌＯ４）６．２Ｈ２Ｏ（１），［Ｃｕ３（４，４＇－ｂｐｙ），（ｂｐｙ）３］（ＣｌＯ４）６．Ｈ２Ｏ（２）和［Ｃｕ３９４，４＇－ｂｐｙ）３．（ＮＯ２－ｐｈｅｎ）３］（ＣｌＯ４）６．６Ｈ２Ｏ（３）。经元素分析，电导，ＩＲ，电子光谱，ＥＳＲ，磁化率等方法进行了表征，推定该配合物具有以４，４’－联吡     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.