含有烯丙基亚胺酚配体的ⅣB族烯烃聚合催化剂以及制备双峰分布聚乙烯(英)

选择含有烯丙基亚胺酚为辅助配体，设计合成了5个ⅣB族钛锆金属络合物[{CH₂=CHCH₂N=CH-C₆H₃(3-R)O}₂MCl₂](4a：R=t-Bu，M=Zr；4b：R=t-Bu，M=Ti；4c：R=Ph，M=Zr；4d：R=Ph，M=Ti)和[{(CH₃)₂CHCH₂N=CH-C₆H₃(3-t-Bu)O}₂ZrCl₂] (5)，对它们进行了红外光谱、核磁共振及元素分析表征。并用X-射线单晶衍射法测定了化合物4a和4d的晶体结构。部分配合物在助催化剂MMAO的作用下对烯烃聚合显示了较好的催化活性，其中自固载催化剂4a生成了双峰分布的聚烯烃产品 (M_w/M_n=15.3～31.9)。     

高电势铁硫蛋白的模型化合物：2，4，6-三苯基苯硫酚的4Fe4S簇合物的合成与性质

新型簇合物(n-Bu₄N)₂［Fe₄S₄(tpbt)₄］(tpbt=2,4,6-三苯基苯硫酚基)通过2，4，6-三苯基苯硫酚和(n-Bu₄N)₂［Fe₄S₄(S-t-Bu)₄］在DMF(二甲基甲酰胺)中进行配体交换反应合成得到。该簇合物在CH相似文献   

膦配体对乙炔羰化制丙烯酸催化剂NiBr2-CuBr2性能的影响

研究了一系列单膦配体（P（L））对NiBr₂-CuBr₂-P（L）催化乙炔羰基化制丙烯酸（AA）性能的影响。结果表明,以三叔丁基膦（P（t-Bu）₃）作配体时催化剂NiBr₂-CuBr₂-P（L）的性能最好。以P（t-Bu）₃为配体、CH₃SO₃H为酸助剂,溴化镍NiBr₂用量为0.001mol,n_NiBr2：n_CuBr2：n_P（t-Bu）3：n_CH3SO3H为1：0.5：1.5：0.5,水用量V_H2=5mL,在反应温度200℃、压力8.0MPa、时间60min时,乙炔的转化率为75.8%、丙烯酸的选择性达到98.6%。NiBr₂-CuBr₂-P（L）-CH₃SO₃H催化剂与NiBr₂-CuBr₂相比具有较高的丙烯酸选择性和收率,解决了传统催化剂选择性低、反应过程产生积碳等问题。     

苯二胺和联苯二胺类叔芳胺的合成及发光性能的研究

N,N′-二苯基-1,4-苯二胺和N⁴,N^4'-二苯基-4,4'-联苯二胺分别与芳基溴在Pd(OAc)₂/P(t-Bu)₃催化下于120 ℃邻二甲苯溶液中反应生成苯二胺和联苯二胺类叔芳胺有机电致发光材料, 这些化合物的熔点都在300 ℃以上. 产物的结构经¹H NMR, ¹³C NMR, ¹³C (DEPT), MS (HREI和EI)表征. 用UV-Vis, PL, DSC测定了苯二胺和联苯二胺类叔芳胺化合物的发光性能.     

含偶磷氮烷配体的三核钌羰基簇合物的合成和晶体结构

用Ru₃(CO)₁₂与顺-2,4二(叔丁基胺基)-1,3,-二(叔丁基)-1,3,2,4-环偶磷氮烷cis-[P(NHBu^t)NBu^t]₂反应,得到两个新的含偶磷氮环的三核钌羰基簇合物:Ru₃(CO)₁₁[{P(NHBu^t)NBu^t}₂] Ⅰ和Ru₃(CO)₁₁[P(NHBu^t)(NBu^t)₂P(O)H] Ⅱ。对它们进行了元素分析,IR和¹H NMR谱表征,并用X-ray单晶衍射法测定了晶体结构。Ⅰ:正交晶系,Pna2(1)空间群,a=2.7574(9) nm,b=0.8981(3) nm,c=1.5272(5) nm, V=3.782(2) nm³,D_c=1.686 g·cm^-3,Z=4;Ⅱ:三斜晶系,P1空间群,a=0.96384(19) nm,b=1.1705(2) nm,c=1.5589(3) nm,α=101.72(3) °,β=91.54(3) °,γ=108.20(3) °,V=1.6282(6)nm³,D_c=1.845g·cm^-3,Z=2;两个簇合物均为Ru₃(CO)₁₂的单取代衍生物,配位基环偶磷氮烷以单齿P原子配位在一个Ru原子的赤道位置上。Ⅱ中,偶磷氮环上未配位P(Ⅲ)被氧化成具有膦酰基结构(=P(O)H)的P(Ⅴ)。     

双核钌-DMBA双芳香炔化合物的合成和电化学性质

在弱碱性条件下,双核钌(III)配合物Ru₂（DMBA）₄（NO₃）₂（DMBA=tetrakis-N,N''-dimethylbenzamidinate）与不同芳香炔反应（其中芳香基团包括：NAP^me,N-甲基-1,8-萘二甲酰亚胺;NAP^iso,N-异丙基-1,8-萘二甲酰亚胺;Naphth,萘;Ant,蒽）,制备了相应的端基炔取代配合物trans-Ru₂（DMBA）₄（C₂Ar）₂（Ar=NAP^me,1;NAP^iso,2;Naphth,3;Ant,4）。利用X射线晶体衍射测定了它们的结构。所有化合物的Ru-Ru键长处于单键范围（0.2450~0.2491 nm）,它们均是抗磁性物质。进一步通过¹H NMR和UV-Vis-NIR光谱进行了表征。电化学研究表明,所有化合物显示出与芳香基团有关的2个可逆的单电子氧化还原过程（包括一个氧化过程和一个还原过程）。     

双核钌-DMBA双芳香炔化合物的合成和电化学性质

在弱碱性条件下,双核钌（Ⅲ）配合物Ru₂（DMBA）₄（NO₃）₂（DMBA=tetrakis-N,N''-dimethylbenzamidinate）与不同芳香炔反应（其中芳香基团包括：NAP^me,N-甲基-1,8-萘二甲酰亚胺;NAP^iso,N-异丙基-1,8-萘二甲酰亚胺;Naphth,萘;Ant,蒽）,制备了相应的端基炔取代配合物trans-Ru₂（DMBA）₄（C₂Ar）₂（Ar=NAP^me,1;NAP^iso,2;Naphth,3;Ant,4）。利用X射线晶体衍射测定了它们的结构。所有化合物的Ru-Ru 键长处于单键范围（0.245 0~0.249 1 nm）,它们均是抗磁性物质。进一步通过¹H NMR和UV-Vis-NIR光谱进行了表征。电化学研究表明,所有化合物显示出与芳香基团有关的2个可逆的单电子氧化还原过程（包括一个氧化过程和一个还原过程）。     

二聚体配合物[(n-Bu)2Sn(C10H8N2O3)(C2H5OH)]2的合成和晶体结构

The novel seven-coordinate complex [(n-Bu)₂Sn(C₁₀H₈N₂O₃)(C₂H₅OH)]₂ (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionic acid benzoyl hydrazone) was synthesized by the reaction of (n-Bu)₂SnO with 2-oxo-propionic acid benzoyl hydrazone in 1∶1 molar ratio in benzene-ethanol (V/V, 3/1), and its structure was characterized by X-ray single crystal diffraction. The crystal belongs to a tetragonal system with space group I4₁/a, a=2.4890(2)nm, b=2.4890(2)nm, c=1.5170(3)nm, V=9.398(2)nm³, Z=8, F(000)=3968, D_c=1.366g·cm^-3, and the structure was refined to final R₁=0.0530, wR₂=0.0971. The structure of the title complex is described as a dimer through weak interactions of Sn…O bonding and hydrogen bond. The tin atoms rendered sev-en-coordination in a distorted pentagonal bipyramid geometry structure, four oxygen atoms [O1, O2, O2^#1 and O4] and one nitrogen atom N2 formed the equatorial plane and C11-Sn1-C15 is the axis. CCDC: 212696.     

基于二羟基萘二磺酸根的配合物Na3[Na5(dhns)2]·(phen)4·2H2O的合成、晶体结构和热稳定性

2,7-二羟基萘-3, 6-二磺酸二钠盐(Na₂H₂dhns)与邻菲罗啉在乙醇/水溶液中自组装得到一新的配合物Na₃[Na₅(dhns)₂]·(phen)₄ ·2H₂O (1),并用CHN元素分析、IR、TGA和X-射线单晶衍射分析进行了表征。晶体属正交晶系, Pna2₁空间群, a=2.829 85(12) nm,b=1.038 99(14) nm, c=2.259 23(13) nm, V=6.642 6(10) nm³, Z=4, D_c=1.573 g·cm^-3, R₁=0.050 6, wR₂=0.124 0, S=1.05。     

二羟基萘二磺酸根构筑的一维链状镉配位聚合物的合成与晶体结构

采用常规溶液挥发法,3,6-二羟基-2,7-萘二磺酸二钠盐(Na₂H₂dhns)、咪唑(imdz)与Cd(NO₃)₂·4H₂O在甲醇-水溶液中反应合成了一种一维镉配位聚合物{[Cd₂(dhns)(imdz)₄]·H₂O}_n(1),并用元素分析、IR、UV、PL和TG等方法进行了表征。经X-射线单晶衍射分析确定了其晶体结构,晶体属单斜晶系,空间群C2/m,晶胞参数a=1.24597(6)nm,b=1.55833(9)nm,c=1.62999(10)nm,β=90.258(6)°,V=3.1648(3)nm³,Z=4,M_r=831.39,D_c=1.745g·cm^-3,μ=1.534mm^-1,F(000)=1640,R=0.0564,wR₂=0.1405,S=1.09。每个Cd(Ⅱ)处于畸变的八面体配位环境,2个八面体共同形成双核金属簇,金属簇经dhns^4-四重桥联形成一维配位聚合物。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.