含dppm桥的双核过渡金属配合物中金属─金属间的相互作用

应用ＥＨＭＯ法研究了一系列含ｄｐｐｍ双二苯基膦甲烷桥的双核过渡金属配合物［ＰｄＢｒ（ｄｐｐｍ）］_２，Ｍ_２Ｃｌ_２（μ－ＣＯ）（ｄｐｐｍ）_２（Ｍ＝Ｐｄ，Ｒｈ），［ＲｈＣｌ（ＣＯ）（ｄｐｐｍ）］_２，Ｍ_２－（μ－Ｃｌ）_２Ｃｌ_４（ｄｐｐｍ）_２（Ｍ＝Ｎｂ、Ｔａ、Ｒｅ、Ｒｕ）的电子结构。根据配合物的成键特征，对其金属－金属的相互作用进行了分析。计算结果可以作为解释这类配合物的某些物理化学性质的理论依据。     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

2-(N-十六烷基氨基甲酰基)-8-羟基喹啉金属配合物的制备及红外光谱研究

合成了新的十一个２－（Ｎ－十六烷基氨基甲酰基）－８－羟基喹啉（Ｃ２６Ｈ３９Ｎ２Ｏ２，简写为ＨＬ）的配合物［ＭＬ２］，（Ｍ＝Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｄ（Ⅱ）、Ｐｄ（Ⅱ）、Ｍｇ（Ⅱ）和Ｃａ（Ⅱ））、［ＭＬ２Ｃｌ（Ｈ２Ｏ）４］（Ｍ＝Ｌａ（Ⅲ）、Ｇａ（Ⅲ））和［ＣｕＬＣｌ］，并经元素分析、摩尔电导、磁性和红外光谱所表征。红外光谱表明：配合物是以三齿形式与金属离子配位。配合物中Ｃ－Ｏ键伸缩振动频率与中心金属离子的相对原子质量或中心离子的电离势呈双线性关系。     

双核钯配合物［Ph_2P（o－C_6H_4CO）PdCl］_2·2CH_2Cl_

合成了双氯桥双核钯配合物［Ｐｈ_２Ｐ（ｏ－Ｃ_６Ｈ_４ＣＯ）ＰｄＣｌ］_２·２ＣＨ_２Ｃｌ_２进行了元素分析、红外光谱表征和晶体结构测定，研究了其催化氢化性能。在３０～８０℃、氢分压１．０～５．０ＭＰａ的范围内。发现该配合物是催化氢化丙烯酸为丙酸的有效催化剂．晶体［Ｐｄ_２Ｃｌ_２（Ｃ_（１９）Ｈ_（１４）ＯＰ）_２］·２ＣＨ_２Ｃｌ_２属Ｐ１空间群，ａ＝０．９３０４（３）ｎｍ，ｂ＝１．０３９２（２）ｎｍ，ｃ＝１．１０６２（３）ｎｍ；ａ＝１０２．７８（２），Ｂ＝９７．３５（３），γ＝９５．２５（２），Ｖ＝１．０２６４ｎｍ~３，Ｍ＝１０３２．１７，２＝１，Ｄｃ＝１．６７０ｇ／ｃｍ~３，ｕ＝１３．６９５ｃｍ~（－１），Ｆ（０００）＝５１２，用１９４５个独立衍射精修结构，最终Ｒ＝０．０３６。     

线型异核三金属M－E－M（M＝Mo，W；E＝Hg，Zn）化合物的研究──［η~5－RC_5H_4（CO）_3M］_2Zn（M＝Mo，W；R＝CO_2Me，CO_2Et）的合成、性质及结构

研究了含汞三金属化合物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｈｇ（Ｍ＝Ｍｏ，Ｗ；Ｒ＝Ｍｅ，Ｅｔ，ＣＯ_２Ｍｅ，ＣＯ_２Ｅｔ）与锌粉的置换反应，发现当取代基Ｒ为给电子的Ｍｅ和Ｅｔ时底物不发生反应，而取代基Ｒ为拉电子的ＣＯ_２Ｍｅ和ＣＯ_２Ｅｔ时，则底物中的汞可被锌置换，生成带有机官能团的三金属化合物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｚｎ；另外，还发现Ｒ为ＣＯ_２Ｅｔ，Ｍ为Ｍｏ的产物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｚｎ可在室温下被分解为相应的氯代物η_５－ＥｔＯ_２ＣＣ_５Ｈ_４ＭｏＣｌ．     

Pd_2X_2（dpm）_2（X＝NCO~－，CH_3CO_2~－，SCN~－，

采用ＮＭＲ方法考察了室温和低温（－７８～－６０℃）下Ｐｄ２Ｘ２（ｄｐｍ）２（Ｘ＝ＮＣＯ－，ＣＨ３ＣＯ，ＳＣＮ－和ＮＯ，ｄｐｍ＝Ｐｈ２ＰＣＨ２ＰＰｈ２）与Ｈ２Ｓ在ＣＤ２Ｃｌ２或ＣＤＣｌ３中的反应。结果表明，在Ｘ＝ＮＣＯ－和ＣＨ３ＣＯ的情况下，Ｈ２Ｓ优先与这些Ｐｄ配合物的阴离子作用生成相应的共轭酸ＨＸ和Ｐｄ２（ＳＨ）２（ｄｐｍ）２，后者在Ｈ２Ｓ存在下又进一步转化为Ｐｄ２（ＳＨ）２（ｄｐｍ）２（μ－Ｓ）；当Ｘ＝ＳＣＮ－和ＮＯ时，反应则生成结构可能为［Ｐｄ２（Ｈ）（ＳＨ）（μ－ＳＨ）（ｄｐｍ）２］＋的双核Ｐｄ配合物。     

含氨茂铁异核金属配合物合成和性质研究

Ｐｄ（Ⅱ）、Ｐｔ（Ⅱ）ＤＭＡＦ配合物已合成，并已定结构。本文采用ＭＸ２（Ｍ－Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）；Ｘ＝Ｃｌ，Ｂｒ，Ｉ）在ＣＨ２Ｃｌ２中和ＤＭＡＦ作用合成［ＭＸ２．２ＤＭＡＦ］型配合物。由ＮｉＣｌ２．２ＤＭＡＦ．Ｃ７Ｈ８晶胞参数推知属于对称链状四配位结构。ＩＲ谱表明，该化合物化学式为ＭＸ２．２ＤＭＡＦ。ＣＶ表明配合物中Ｍ（Ⅱ）和Ｆｅ（Ⅱ）存在。由于金属离子互相影响。Ｅｐ／２     

新型含钌异核过渡金属簇合物的合成及其结构表征

利用金属交换法合成了四个新的含钌手性过渡金属簇合物［ＭＲｕＣｏ（ＣＯ）_８（μ_３－Ｓｅ）［η_５－Ｃ_５Ｈ_４Ｃ（Ｏ）Ｒ｝］（ １ Ｍ＝ Ｍｏ, Ｒ＝ ＯＥｔ; ２ Ｍ＝ Ｗ, Ｒ＝ ＯＥｔ; ３ Ｍ＝ Ｍｏ, Ｒ＝ ＣＨ_２ＣＨ_２ＣＯＯＭｅ; ４ Ｍ＝ Ｗ, Ｒ＝ ＣＨ_２ＣＨ_２ＣＯＯＭｅ）,并用红外、核磁、元素分析测试结果进行表征,对簇合物１进行了单晶结构测定,晶体属单斜晶系,Ｐ２_１／ｎ空间群,晶胞参数ａ＝１０．１６８（２）Ａ,ｂ＝９．０１８（２）Ａ,ｃ＝２３．１２１（３）Ａ,β＝９２．５０（１）°,Ｚ＝４。     

［Mn_2（bzacen）_2（MeOH）_2（μ－4，4′－bipy）］（ClO_4）_2的合成、结构和谱学性质

合成了［Ｍｎ_２（ｂｚａｃｅｎ）_２（ＭｅＯＨ）_２（μ－４，４′－ｂｉｐｙ）］（ＣｌＯ_４）_２化合物，并测定其晶体结构。该晶体属单斜晶系，空间群Ｐ２_１／ｎ，晶胞参数：ａ＝１．３０８２（３）ｎｍ，ｂ＝１．２７１３（３）ｎｍ，ｃ＝１．８００６（５）ｎｍ，β＝１１０．９１（２）°，Ｚ＝２，μ＝５．９７ｃｍ－１，Ｒ＝０．０５８０，ＧＯＦ＝１．６６．在配合物阳离子中，４，４′－联吡啶桥联２个［Ｍｎ（ｂｚａｃｅｎ）（ＭｅＯＨ）］＋，而锰原子具有３个Ｎ原子和３个Ｏ原子形成的扭曲八面体配位构型。红外光谱和拉曼光谱均表明，形成配合物后，ｖ_（Ｃ＝Ｎ）、ｖ（Ｃ＝Ｏ）、和ｖ（Ｃ＝Ｃ）移向低频。红外光谱的１１１０ｃｍ￣（－１）谱带表明ＣｌＯ_４￣－未与Ｍｎ（Ⅲ）配位，８１２ｃｍ￣（－１）振动说明４，４′－ｂｉｐｙ充当桥联二齿配体。拉曼光谱中的４６３ｃｍ￣（－１）和４０１ｃｍ￣（－１）别为Ｍｎ－Ｏ和Ｍｎ－Ｎ的振动带。电子光谱证明存在ｄ－ｄ、ｄ－π和π－π跃迁。电极电位测定显示该配合物Ｍｎ（Ⅲ）的价态是稳定的。     

等瓣置换反应的研究──手性簇合物［（η~5－MeO_2CC_5H_4）（CO）_2Mo］·［（η~5－MeO_2CC_5H_4）（CO）_2W］Fe（CO）_3（μ_3－S）的分子结构及晶体结构

用Ｘ射线衍射法测定了由η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_３ＭｏＮａ和［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｗ］Ｆｅ－（ＣＯ）_３Ｃｏ（Ｃｏ）_３（μ_３－Ｓ）的等瓣置换反应所生成的手性簇合物──［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｍｏ］－［（η~５－ＭｅＯ_２ＣＣ_５Ｈ_４）（ＣＯ）_２Ｗ］Ｆｅ（ＣＯ）_３（μ_３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数α＝０．８７１６２（５）ｎｍ，ｂ＝０．７６２１８（４）ｎｍ，ｃ＝１．８７１１１（８）ｎｍ；α＝９４．１６４（４）°，β＝９７．９７９（２）°，γ＝９９．１０８（２）°，Ｚ＝２，μ＝５．９ｃｍ~（－１）。最终的一致性因子Ｒ＝０．０３６，Ｒｗ＝０．０３７．该簇合物含ＭｏＷＦｅＳ四面体簇核，其中Ｍｏ、Ｗ原子以１：１的比例无序地分占了四面体的２个顶点．     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.