单取代环戊二烯基羰基钼化合物的合成、晶体结构及热稳定性研究

单取代环戊二烯(C₅H₅R)(R=n-Butyl (1), Benzyl (2), n-Propyl (3), Allyl (4))分别和Mo(CO)₆反应, 生成4个新的环戊二烯基钼双核羰基配合物(C₅H₄R)₂Mo₂(CO)₆(R=n-Butyl (5), Benzyl (6), n-Propyl (7), Allyl (8))。配合物5~8通过元素分析, IR, 1H NMR, 热重进行了表征, 并用X-ray单晶衍射法测定了配合物5和6的晶体结构。晶体结构显示配合物5属于单斜晶系, P2₁/c空间群, 配合物6属于三斜晶系, P1空间群;热重分析表明配合物5和6分别处于107和162℃以下温度时很稳定。     

取代四甲基环戊二烯基钌羰基化合物的合成及晶体结构(英文)

The ligands (C5Me4R) [R =n-Butyl (1), Benzyl (2), PhMe-2 (3)] reacted with Ru3(CO)12 in refluxing xylene to give corresponding new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes [(η5-C5Me4R)Ru(CO)( μ-CO)]2 [R=n-Butyl (4), Benzyl (5), PhMe-2 (6)], respectively. The three new complexes were characterized by elemental analysis, IR and 1H NMR spectra. The crystal structure of complex 5 was determined by single crystal X-ray diffraction. The X-ray crystal structure of complex 5 confirms the structure with bridging and terminal CO groups. CCDC: 709601.     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

二(1-环戊烯基茚基)四羰基二钌的合成、晶体结构及热稳定性研究

由6,6-四亚甲基苯并富烯C9H6C(CH2)4与Ru3(CO)12在二甲苯中加热回流,合成了一个钌配合物[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]。通过元素分析、红外、热重、核磁共振进行了表征及研究。用X射线单晶衍射法测定了[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]的结构,结果表明:晶体属于单斜晶系,P21/c空间群,a=0.757 1(13)nm,b=1.577 7(3)nm,c=1.107 3(19)nm,β=90.07(2)°,V=1.322 6(4)nm3,Dc=1.699 g.cm-3,μ=1.179 mm-1,F(000)=676,Z=2,R1=0.030 5,wR2=0.072 4。     

多(三甲硅基)取代环戊二烯基二羰基钼环卡宾配合物的合成和结构

三(三甲基硅基)环戊二烯在一缩二乙二醇二甲醚或四氢呋喃中经n-BuLi处理后, 随之与Mo(CO)6加热, 生成相应的环戊二烯基羰基钼负离子锂盐[η^5-{(Me3Si)3C5H5-n}Mo^-(CO)3]Li^+(n=2, 3)(1), 同时观察到有脱硅基现象发生。1与X(CH2)3X在一缩二乙二醇二甲醚中反应, 无论X=I或Br, 均生成标题化合物[X=I: n=3(2), n=2(3); X=Br: n=3(4), n=2(5)]。1与X(CH2)3X的反应如在THF中进行, 则只有当X=I时才能生成环卡宾钼配合物。以元素分析, IR, 1H NMR和13C NMR表征了2-5的结构, 并用X射线衍射测定了4的晶体结构。晶体属单斜晶系,空间群为P21/n, 晶胞参数a=1.2611(3), b=1.2434(2),c=1.7095(6)nm, β=91.07(2)°, V=2.680(2)nm^3,Dc=1.563g.cm^-^3, Z=4, 最终偏差因子R=0.062, Rw=0.054.     

含柠檬酸配体的钼硫簇合物的合成与晶体结构的测定

合成了含有Mo—S簇阴离子 [Mo2 O2 ( μ S) 2 (C6H5O7) (C6H4 O7) ]5-柠檬酸簇合物 ,并通过元素分析、红外光谱、紫外 可见光谱和X射线光电子能谱对配合物进行了表征 ,用X射线衍射法测定了该化合物的晶体结构 .结果表明 ,该簇合物属于单斜晶系 ,空间群P2 1/c,a =2 3 766( 5)nm ,b =1 3 2 74 ( 3 )nm ,c =2 2 4 71 ( 5)nm ,α=γ =90°,β=1 1 8 2 1°,V =6 2 4 7( 2 )nm3 ,Z =8,一致性因子R =0 0 83 1 ,R2 ,w=0 1 536.该簇合物阴离子中每一个Mo原子都采取扭曲的八面体结构 ,柠檬酸通过羟基、α 羧基、一个 β 羧基与Mo配位 .晶体结构表明在一个结晶学上不对称的结构单元内有两个结晶学上独立的分子 .     

基于两个取代四甲基环戊二烯基配体的金属羰基化合物的合成及晶体结构(英文)

配体[C5Me4HR][R=4-Br Ph(1),(Me C5H3N)CH2(2)]分别与Mo(CO)6,Ru3(CO)12和Fe(CO)5在二甲苯中加热回流,得到了6个双核配合物trans-[η5-C5Me4R]2Mo2(CO)6(3,4),trans-[(η5-C5Me4R)Ru(CO)(μ-CO)]2(5,6)和trans-[η5-(C5Me4R)Fe(CO)(μ-CO)]2(7,8)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物3,5,6和8的结构。     

含SR桥的双核钼(I)配合物Mo2(CO)8-n(SR)2Ln的新合成途径和Mo2(C(O)6(SPh)2(MeCN)2的结构研究

经由零价双核钼含SR桥的配合物的氧化反应合成了一系列含各种SR桥的双核钼(I)配合物Mo2-(CO)8-n(μ-SR)2Ln(R=Br^t, Ph, Bz(C6H5CH2), CH2CO2Et;L=MeCN, PPh3; n=0,2]. 并应用红外光谱、元素分析等进行表征, 讨论了新的合成途径. 含MeCN配位体配位到Mo(I)上的配合物, Mo2(CO)6(SPh)2(MeCN)2经X射线结构测定, 系属单斜晶系, 空间群P21/c,a=9.241(2), b=9.330(3), C=15.458(4)A:β=105.77(2)°V=1283(1)A^3; Z=2; R=0.033. Mo-Mo距离为2.978A, 表明其Mo-Mo距离为2.978A, 表明其Mo-Mo键的形成, Mo-S键长为2.469A. 比较同系物Mo2(CO)8(μ-SCH2CO2-Et)2, Mo2(CO)6(μ-SCH2CO2Et)2(MeCN)2和Mo2(CO)8(μ-SBu^t)2的结构, 并讨论其结构与化学.     

含SR桥的双核钼(I)配合物Mo2(CO)8-n(SR)2Ln的新合成途径和Mo2(C(O)6(SPh)2(MeCN)2的结构研究

经由零价双核钼含SR桥的配合物的氧化反应合成了一系列含各种SR桥的双核钼(I)配合物Mo2-(CO)8-n(μ-SR)2Ln(R=Br^t, Ph, Bz(C6H5CH2), CH2CO2Et;L=MeCN, PPh3; n=0,2]. 并应用红外光谱、元素分析等进行表征, 讨论了新的合成途径. 含MeCN配位体配位到Mo(I)上的配合物, Mo2(CO)6(SPh)2(MeCN)2经X射线结构测定, 系属单斜晶系, 空间群P21/c,a=9.241(2), b=9.330(3), C=15.458(4)A:β=105.77(2)°V=1283(1)A^3; Z=2; R=0.033. Mo-Mo距离为2.978A, 表明其Mo-Mo距离为2.978A, 表明其Mo-Mo键的形成, Mo-S键长为2.469A. 比较同系物Mo2(CO)8(μ-SCH2CO2-Et)2, Mo2(CO)6(μ-SCH2CO2Et)2(MeCN)2和Mo2(CO)8(μ-SBu^t)2的结构, 并讨论其结构与化学.     

3-羟基-1-金刚烷甲酸轻稀土配合物的合成、晶体结构及与DNA作用

以3-羟基-1-金刚烷甲酸(Hhata=C11H16O3),邻菲啰啉(phen)和稀土硝酸盐为原料,合成了7个轻稀土配合物(1)～(7)[RE2(hata)6(phen)2].4H2O(RE=La(1),Ce(2),Pr(3),Nd(4),Sm(5),Eu(6),Gd(7))。其中(1)为单晶样,其余6个样为粉末样;用元素分析、红外光谱、摩尔电导、热重分析等手段表征了配合物;用单晶X射线衍射法测定了(1)的晶体结构,该配合物[La2(hata)6(phen)2].4H2O(C90H114La2N4O22)属于单斜晶系,空间群P2(1)/c,a=1.33979(13)nm,b=2.6395(2)nm,c=1.31321(14)nm,β=112.174(4)°,V=4.3005(7)nm3,Z=2,Mr=1881.67,F(000)=1944.0,Dc=1.453 g.cm-3,μ(Mo Kα)=1.056 mm-1。结果表明:两个镧原子与两个邻菲啰啉中的4个氮原子和6个3-羟基-1-金刚烷甲酸根中的羧基氧原子配位,中心原子的配位数为9。用溴化乙锭荧光探针法测试了7个配合物对EB-DNA复合体系的荧光猝灭效应,实验结果显示配合物均与DNA发生了不同程度的插入作用。     

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%).     

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.     

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.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

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.