五羰基乙酰基锰的深度氢硅烷化

采用两步法合成(CO)₅MnCOCH₃ (1), 然后对1与Me₂PhSiH的深度氢硅烷化反应做9 h的¹H NMR连续监控, 通过将反应物和衍生物的特征峰与内标物C₆H₅(CH₂)₂C₆H₅的特征峰对照直接积分定量, 得到适时含量(mmol)随反应时间改变(h)的变化规律。期间共得到了9种中间体或最终产物, 通过核磁波谱对比, 确定了这些化合物的分子结构。除了对其中6种化合物的特征峰积分直接定量外, 对另外3个化合物采用化学计量结合特征峰积分间接定量, 并对其反应机理做出了合理的解释。最后提出了深度氢硅烷化的多步反应与双通道机理, 并且对反应原料1和Me₂PhSiH中Mn和Si进行了全程跟踪, 结果发现, 在9 h时, Mn总含量高达90.7%, 而Si总含量高达91.4%。     

桥联8-氨基喹啉衍生物及其锆化合物的合成及结构

以8-氨基喹啉和8-喹哪啶为原料,通过锂化再与二甲基二氯硅烷反应,分别得到对称的桥联配体Me₂Si[NH（C₉H₆N）]₂（1a）,Me₂Si[NCH₃（C₉H₅N）]₂（1b）。1a和1b分别与2倍物质的量的正丁基锂反应,然后与ZrCl₄作用得到2种配位模式不同的硅桥联取代8-氨基喹啉锆化合物Zr{Me₂Si[N（C₉H₆N）]₂}₂（2）和Zr{Me₂Si[NCH₃（C₉H₅N）]₂}Cl₂（3）。化合物1~3通过¹H NMR、¹³C NMR和元素分析进行表征,2和3通过X-射线单晶衍射确定其晶体结构。结果表明化合物2的中心Zr原子与8个N原子配位,属于变形十二面体结构,单晶属于三斜晶系;化合物3的中心Zr原子与4个N原子和2个Cl原子配位,属于变形八面体,单晶属于正交晶系。     

受限几何型金属化合物的合成和催化性能

通过筛选合成路线和方法制备了3种桥联芴基-芳胺基化合物Me₂Si[（Flu）H]NH-2,6-ⁱPr₂C₆H₃（L¹）、Me₂Si[2,7-^tBu₂Flu（H）]NH-2,6-ⁱPr₂C₆H₃（L²）和Me₂Si[2,7-^tBu₂Flu（H）]NH-2,4,6-Me₃C₆H₂）（L³）,分别与第四族金属氯化物MCl₄反应制备了4种受限几何结构的茂金属化合物[Me₂Si（Flu）（N-2,6-ⁱPr₂C₆H₃）]ZrCl₂（THF）₂（1）、[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]TiMe₂（2）、[Me₂Si（2,7-^tBu₂Flu）（N-2,4,6-Me₃C₆H₂）]TiMe₂（3）和[Me₂Si（2,7-^tBu₂Flu）（N-2,6-ⁱPr₂C₆H₃）]HfMe₂（4）。化合物L¹~L³和1~4都经过谱学和元素分析表征,其中1~3还经过X射线衍射单晶结构确认。在AlⁱBu₃和（Ph₃C）⁺[B（C₆F₅）₄]-双助剂作用下研究了1~4分别催化乙烯/1-辛烯聚合性能,结果显示茂金属单活性中心作用特点以及1-辛烯的共聚效果。考察和比较了其它3种受限几何钛化合物[Me₂Si（C₅Me₄）（N^tBu）]TiCl₂、[Me₂Si（Ind）（N^tBu）]TiCl₂和[Me₂Si（Flu）（N^tBu）]TiMe₂的催化性能;讨论了1~4的结构和催化作用的关联性。     

含硅铁键环状化合物[Me2Si-η5-C5H4Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe- (CO)2－n(PPh3)n] (n＝0或1)的合成与结构

鉴于含硅-过渡金属键化合物作为催化剂具有重要的应用价值, 在我们最近发现的化合物(η⁵,η⁵-C₅H₄Me₂SiSi-Me₂C₅H₄)Fe₂(CO)₄ (1)的硅硅键和铁铁键复分解重排反应可以有效地合成含有两个硅铁键的环状化合物[Me₂Si-η⁵-C₅H₄- Fe(CO)₂]₂ (2)的基础上, 对该硅铁键环状化合物的三苯基膦取代衍生物[Me₂Si-η⁵-C₅H₄-Fe(CO)(PPh₃)][Me₂Si-η⁵-C₅H₄Fe(CO)_2－n(PPh₃)_n] (3: n＝0, 5: n＝1)的合成方法进行了研究. 发现化合物1在三苯基膦存在下的复分解重排反应是合成单三苯基膦取代产物3的最好方法; 而双三苯基膦取代化合物5则可通过光照条件下2与三苯基膦发生羰基取代反应而得到, 产物中含有的顺反异构体可利用制备薄层色谱法分离. 利用X射线衍射法测定了化合物3的分子结构, 考察了三苯基膦配体的存在对分子结构的影响以及三苯基膦与铁形成的配位键的稳定性.     

苯基或联苯基桥连双环戊二烯基铼羰基化合物的合成、结构及催化性能

两个单桥连的双环戊二烯（C₅Me₄H）E（C₅Me₄H）（E=C₆H₄,（C₆H₄）₂）分别与Re₂（CO）₁₀在均三甲苯中加热回流,得到了2个双核配合物（E）[（η⁵-C₅Me₄）Re（CO）₃]₂（E=C₆H₄（1）,（C₆H₄）₂（2））。通过元素分析、红外光谱、核磁共振氢谱和碳谱对配合物1和2的结构进行了表征,用X射线单晶衍射分析测定了配合物的结构。同时对2个配合物在芳香族化合物Friedel-Crafts酰基化反应中的催化活性进行了研究。     

苯基或联苯基桥连双环戊二烯基铼羰基化合物的合成、结构及催化性能

两个单桥连的双环戊二烯（C₅Me₄H） E（C₅Me₄H）（E=C₆H₄,（C₆H₄）₂）分别与Re₂（CO）₁₀在均三甲苯中加热回流,得到了2个双核配合物（E）[（η⁵-C₅Me₄） Re（CO）₃]₂（E=C₆H₄（1）,（C₆H₄）₂（2））。通过元素分析、红外光谱、核磁共振氢谱和碳谱对配合物1和2的结构进行了表征,用X射线单晶衍射分析测定了配合物的结构。同时对2个配合物在芳香族化合物Friedel-Crafts酰基化反应中的催化活性进行了研究。     

新型的含硫族元素碳硼烷配体的三(3，5-二甲基-1-吡唑)硼氢钼配合物的合成和分子结构(英)

三齿单核三(3，5-二甲基-1-吡唑)硼氢钼配合物Tp^*Mo(O)Cl₂ (1)(Tp^*=三(3，5-二甲基-1-吡唑)硼氢HB(C₃H(Me₂)N₂)₃)与含硫族元素碳硼烷的锂盐[(THF)₂LiE₂C₂B₁₀H₁₀(THF)]<     

2-苯亚胺官能化吲哚基铕-胺基配合物与芳基取代甲脒的反应性

2-（苯亚胺基次甲基）吲哚铕-胺基配合物[η¹：η¹-2-（C₆H₅NH=CH）C₈H₅N]₂Eu[N（SiMe₂）₂]（1）与二芳基取代甲脒（2,6-R₂C₆H₃N=CHNH（C₆H₃R₂-2,6）（R=ⁱPr（2）,Me（3））经过配体交换反应,分别得到了含吲哚基脒基铕配合物[η¹：η¹-2-（C₆H₅NH=CH）C₈H₅N]Eu[（η³-2,6-ⁱPr₂C₆H₃）N=CHN（C₆H₃ⁱPr₂-2,6）][N（SiMe₂）₂]（4）和含脒基的稀土铕配合物[（η³-2,6-Me₂C₆H₃）N=CHN（C₆H₃Me₂-2,6）]₂Eu[N（SiMe₂）₂]（5）。结果表明,脒基的位阻显著影响了吲哚基稀土金属胺基配合物与二芳基取代甲脒的配体交换反应。配合物4和5通过IR、元素分析和X射线单晶衍射分析进行了表征。     

2-苯亚胺官能化吲哚基铕胺基配合物与芳基取代甲脒的反应性

2-（苯亚胺基次甲基）吲哚铕胺基配合物[η¹：η¹-2-（C₆H₅NH=CH）C₈H₅N]₂Eu[N（SiMe₃）₂]（1）与二芳基取代甲脒（2,6-R₂C₆H₃N=CHNH（C₆H₃R₂-2,6）（R=ⁱPr（2）,Me（3））经过配体交换反应,分别得到了含吲哚基脒基铕配合物[η¹：η¹-2-（C₆H₅NH=CH）C₈H₅N]Eu[（η³-2,6-ⁱPr₂C₆H₃）N=CHN（C₆H₃ⁱPr₂-2,6）][N（SiMe₃）₂]（4）和含脒基的稀土铕配合物[（η³-2,6-Me₂C₆H₃）N=CHN（C₆H₃Me₂-2,6）]₂Eu[N（SiMe₃）₂]（5）。结果表明,脒基的位阻显著影响了吲哚基稀土金属胺基配合物与二芳基取代甲脒的配体交换反应。配合物4和5通过IR、元素分析和X射线单晶衍射分析进行了表征。     

半夹芯16电子碳硼烷化合物Me4CpCoS2C2B10H10与二茂铁炔酮的反应性

邻位碳硼烷分别与正丁基锂、硫粉和Me₄CpCo(CO)I₂反应合成得到半夹芯16电子碳硼烷化合物Me₄CpCoS₂C₂B₁₀H₁₀ (1).1与二茂铁炔酮在二氯甲烷中反应得到产物{(Me₄CpCoS₂C₂B₁₀H₁₀)[FcC(O)CHCCHCC(O)Fc]} (2)(Fc=二茂铁基).2是一个1:2的加成产物,2个二茂铁炔酮分子以头-尾的方式加成到分子1中的1个Co-S键上.1和2分别用红外、核磁、元素分析、质谱和单晶X-射线衍射等表征方法进行了结构表征.     

Syntheses,crystal structures,and electrochemistry of novel Fe2SN and FeSN carbonyl complexes with pendant bases

Reactions of Fe₂(CO)₉ with thioacylhydrazones ArCH=NNHCSPh in THF afford Fe₂(CO)₆(μ-κ²S:κ²N-PhC(S)=NNCHArCHArN(CHAr)N=CSPh) (1, Ar?=?C₆H₅; 3, Ar?=?4-CH₃C₆H₄) and Fe(CO)₃(κ²S:N-PhC(=S)NHNCHArCHArN(CHAr)N=CSPh) (2, Ar?=?C₆H₅; 4, Ar?=?4-CH₃C₆H₄). They have been characterized by elemental analyses, IR, ¹H NMR, and ¹³C NMR and structurally determined by X-ray crystallography. Electrochemical studies reveal that when using HOAc as a proton source, they exhibit high catalytic H₂-production.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了 3 个有机锡 9-芴酮-4-甲酸酯:三苯基锡 9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)] (1)、三环己基锡 9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)] (2)和三(2-甲基-2-苯基丙基)锡 9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)] (3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和 ¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗癌活性研究。结果显示:化合物1为一维链状结构,中心锡原子为五配位的畸变三角双锥构型;化合物2和3均为单核分子,锡原子均为四配位的畸变四面体构型。化合物对人宫颈癌细(HeLa)、人肝癌细胞(HUH-7)、人非小细胞肺癌细胞(A549)、人肺腺癌细胞(H1975)和人乳腺癌细胞(MCF-7)都有较好的抑制活性。     

Untersuchungen zur reaktivität von metall-π-komplexen : XVIII. Elektrophile und nucleophile additionsreaktionen an siebenringliganden in tricarbonylmolybdän-komplexen: Synthese von [C7H9Mo(CO)3]BF4, C7H9Mo(CO)3Cl und [C7H9P(C6H5)3]BF4

C₇H₈Mo(CO)₃ reacts with HBF₄ and HCl by protonation of the ring ligand and formation of [C₇H₉Mo(CO)₃]BF₄ (I) and C₇H₉Mo(CO)₃Cl (II), respectively. The compounds are characterised by means of their IR and NMR data. The reaction of I with P(C₆H₅)₃ does not lead, as expected, to [C₇H₉Mo(CO)₃P(C₆H₅)₃]BF₄ (III) but to the phosphonium salt [C₇H₉P(C₆H₅)₃]BF₄ (IV), i.e. nucleophilic addition of the phosphine at the cycloheptadienyl group takes place. The structure of IV has been determined by ¹³C NMR measurements.     

Enantioselective transfer hydrogenation of pro-chiral ketones catalyzed by novel ruthenium and iridium complexes of well-designed phosphinite ligand

Abstract

The interaction of [Ru(η⁶-arene)(μ-Cl)Cl]₂ and Ir(η⁵-C₅Me₅)(μ-Cl)Cl]₂ with a new Ionic Liquid-based phosphinite ligand, [(Ph₂PO)-C₆H₉N₂Ph]Cl, (2) gave [Ru((Ph₂PO)-C₆H₉N₂Ph)(η⁶-p-cymene)Cl₂]Cl (3), [Ru((Ph₂PO)-C₆H₉N₂Ph)(benzene)Cl₂]Cl (4) and [Ir((Ph₂PO)-C₆H₉N₂Ph)(C₅Me₅)Cl₂]Cl (5), complexes. All the compounds were characterized by a combination of multinuclear NMR and IR spectroscopy as well as elemental analysis. Furthermore, the Ru(II) and Ir(III) catalysts were applied to asymmetric transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with good activity (up to 55% ee and 99% conversion) under mild conditions. Notably, [Ir((Ph₂PO)-C₆H₉N₂Ph)(C₅Me₅)Cl₂]Cl (5) is more active than the other analogous complexes in the transfer hydrogenation (up to 81% ee).     

Fluorescent aluminum chelate complexes as modified precursors for nano-structured alumina

A series of new mononuclear heteroleptic derivatives of aluminum(III), {[(CH₃COCHCOCH₃)AlL] (1 and 4)}, {[(C₆H₅COCHCOC₆H₅)AlL] (2, 5, and 7)}, and {[(C₉H₆NO)AlL] (3 and 6)}, have been synthesized by reacting Al(OPrⁱ)₃ with tridentate Schiff base H₂L^x (H₂L¹ = C₁₃H₁₀BrNO₂; H₂L² = C₁₄H₁₃NO₃; H₂L³ = C₁₇H₁₃NO₂) and β-diketone/8-hydroxyquinoline (β-diketone = acetylacetone/dibenzoylmethane) in 1?:?1?:?1 stoichiometry using anhydrous benzene and ethanol. All the complexes were characterized by elemental analysis, FTIR, and NMR (¹H and ¹³C) spectral studies. Molecular structures obtained from single-crystal XRD of aqua 1 (1a) and DMSO coordinated 2 (2a) authenticate their existence. Further, nanostructured α-alumina was synthesized from 1 by well-established sol–gel method and was characterized by powder XRD, TEM, and EDX analyses.     

Supramolecular organotin(IV) dithiocarboxylates as potential antimicrobial agents

A series of tri-, chlorodi-, and diorganotin(IV) derivatives of 4-(2-methoxyphenyl)piperazine-1-carbodithioate (L) {R?=?n-C₄H₉ (1), C₆H₁₁ (2), CH₃ (3) and C₆H₅ (4)}, (n-C₄H₉)₂SnClL (5) and R₂SnL₂ {R?=?n-C₄H₉ (6), C₂H₅ (7), CH₃ (8)} have been synthesized by refluxing organotin(IV) chlorides with the ligand-salt in the appropriate molar ratio. Elemental analysis, Raman, IR, multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn), mass spectroscopic, and single-crystal X-ray crystallographic studies were undertaken to elucidate the structures of the new compounds both in solution and in the solid state. The X-ray diffraction work reveals supramolecular structures for 4 and 6, with distorted trigonal-bipyramidal and distorted octahedral geometries around Sn, respectively. The ligand and several of the new compounds are good antimicrobial agents.     

Synthesis and structural characterization of ferrocenyl indenyl derivatives

In this study, four ferrocenyl indenyl derivatives, C₉H₇–C≡C–Fc (1), C₉H₇–C≡C–Ph–Fc (2), C₉H₇–C≡C–Ph–C≡C–Fc (3), and C₉H₇–Ph–C≡C–Fc (4) (where C₉H₇=indenyl; Fc=C₅H₅FeC₅H₄; Ph=C₆H₅), have been synthesized by Sonogashira and Suzuki cross-coupling reactions and characterized by elemental analysis, and FT-IR, ¹H, ¹³C-NMR, and MS spectroscopic methods, respectively. The molecular structures of 1, 2, and 4 were determined by X-ray single crystal diffraction. Two molecules appeared in the crystal structure of 4, and they interact through an intermolecular hydrogen bond. The electrochemical redox potential differences in 1–4 were investigated using cyclic voltammetry and calculations.     

Synthesis,structural characterization,and in vitro antimicrobial properties of salicylate and pyrazoline complexes of bismuth(III)

Displacement reactions of dichlorobismuth(III)pyrazolinates with oxygen donors such as sodium salicylate and acetate in 1?:?1 and 1?:?2 molar ratio in refluxing anhydrous benzene yields (C₁₂H₁₅N₂OX)Bi(C₆H₄O₃), (CH₃COO)BiCl(C₁₅H₁₂N₂OX), and (CH₃COO)₂Bi(C₁₅H₁₂N₂OX) [C₁₂H₁₅N₂OX?=?3(2′-hydroxyphenyl)-5-(4-X-substituted phenyl) pyrazoline X?=?H in 1,5,9, CH₃ in 2,6,10, OCH₃ in 3,7,11, and Cl in 4,8,12, respectively, (C₆H₄O₃)?=?salicylate and (CH₃COO)?=?acetate]. Newly synthesized derivatives are brown solids, soluble in organic solvents like benzene, chloroform, and acetone. The compounds have been characterized by elemental analyses (C, H, N, Cl, and Bi), molecular weight measurements, and spectral (IR, ¹H NMR, ¹³C NMR) studies. The (C₁₂H₁₅N₂OX) and (C₆H₄O₃) are bidentate while (CH₃COO) is monodentate to bismuth(III), leading to a distorted trigonal bipyramidal structure. The complexes were screened against different bacteria and fungi showing potential antibacterial and antifungal activities.