Growth of Aligned Carbon Nanotubes on Large Scale by Methane Decomposition with Deactivation Inhibitor

The effects of additives containing iron or nickel during chemical vapor deposition(CVD)on the growth of carbon nanotubes(CNTs)by methane decomposition on Mo/MgO catalyst were investigated. Ferrocene and nickel nitrate were introduced as deactivation inhibitors by in-situ evaporation during CVD. The precisely controlled in-situ introduction of these inhibitors increased the surface renewal of catalyst, and therefore prevented the catalyst from deactivation.Using this method,aligned multi-walled CNTs with parallel mesopores can be produced on a large scale.     

Synthesis of biologically active compounds based on 2-ferrocenylmethylene-3-quinuclidone

Biologically active nitrogen heterocycles (1–7) containing ferrocene and quinuclidine fragments were synthesized. 3-Methylene-2-ferrocenylmethylenequinuiclidine forms adducts withN-phenylimides of azodicarboxylic (the structure was established by X-ray structural analysis) and malefic acids. 3-Methylene-2-fer-rocenylmethylenequinticlidine also undergoes [4+2]-cyclodimerization when heated and adds salts of the 3-methyl-2-ferrocenylmethyleneI-azoniabicyclo[2.2.2]oct-3-yl cation at the terminal methylene group to form a linear addition product.Instituto de Quimica, Universidad Nacional Autonoma de Mexico (UNAM), Circuito Exterior, Ciudad Universitaria, Coyoacan.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp 2743–2750, November, 1996.     

取代二茂铁多碘化合物的合成`表征和穆斯堡尔谱研究

合成了一系列新的取代二茂铁多碘化合物,通式为[(RC_5H_4)(R′C_5H_4)Fe]·I_x。元素分析表明,取代基不同时,二茂铁与碘可以整比或非整比结合。~(57)Fe穆斯堡尔谱和红外光谱的研究表明,因取代基不同,二茂铁可以完全地或部分地被碘氧化。     

Comparative reactivity studies of dppf-containing CpRu and (C6Me6)Ru complexes towards different donor ligands (dppf=1,1-bis(diphenylphosphino)ferrocene)

[CpRu(dppf)Cl] (Cp=η⁵-C₅H₅) (1) and [(HMB)Ru(dppf)Cl]PF₆ ((HMB)=η⁶-C₆Me₆) (3) react with different donor ligands to give rise to N-, P- and S-bonded complexes. The stoichiometric reactions of 1 and 3 with NaNCS give the mononuclear complexes [CpRu(dppf)(NCS)] (2) and [(HMB)Ru(dppf)(NCS)]PF₆ (4), respectively, in yields above 80%, while 3 also gives a dppf-bridged diruthenium complex [(HMB)Ru(NCS)₂]₂(μ-dppf) (5) in 67% yield from reaction with four molar equivalents of NaNCS. Compound 5 is also obtained in 70% yield from the reaction of 4 with excess NaNCS. With CH₃CN in the presence of salts, both 1 and 3 give their analogous solvento derivatives [CpRu(dppf)(CH₃CN)]BPh₄ (6) and [(HMB)Ru(dppf)(CH₃CN)] (PF₆)₂ (7). With phosphines, the reaction of 1 gives chloro-displaced complexes [(CpRu(dppf)L]PF₆ (L =PMe₃ (8), PMe₂Ph(9)), whereas the reaction of 3 with PMe₂Ph leads to substitution of dppf, giving [(HMB)Ru(PMe₂Ph)₂Cl] PF₆ (10). The reaction of 1 with NaS₂CNEt₂ gives a dinuclear dppf-bridged complex [{CpRu(S₂CNEt₂)}₂(μ-dppf)] (11), whereas that of 3 results in loss of the HMB ligand giving a mononuclear complex [Ru(dppf)(S₂CNEt₂)₂] (12). With elemental sulfur S₈, 1 is oxidized to give a dinuclear CpRu^III dppf-chelated complex [{CpRu(dppf)}₂(μ-S₂)](BPh₄)Cl (13), whereas 3 undergoes oxidation at the ligand, giving a dppf-displaced complex [(HMB)Ru(CH₃CN)₂Cl]PF₆ (14) and free dppfS₂. The structures of 1, 2, 5-9, 11, 13 and 14 were established by X-ray single crystal diffraction analyses. Of these, 5 and 11 both contain a dppf-bridge between Ru^II centers, while 13 is a dinuclear CpRu^III disulfide-bridged complex; all the others are mononuclear. All complexes obtained were also spectroscopically characterized.     

二茂铁衍生物电子传递剂键合的溶胶-凝胶葡萄糖生物传感器

The sol-gel derived glucose biosensor was developed, and the sol-gel membrane was organically modified by N-（3-triethoxysilylpropyl）-ferrocenylmethylamine （FcSi） as sol-gel precursor to make electrochemical biosensor. The structure of biosensor was sol-gel/FcSi＋GOx/GC type （glucose oxidase, GOx）. The ferrocene mediator was chemically immobilized to the silane network, and GOx was entrapped to the sol-gel glass network. Therefore, these structures prevented mediator leakage and retained the enzyme activity. Additionally, pH of electrolyte, temperature effects, and interference of positive substances with biosensor were investigated. And the electrochemical performance of biosensor was studied by amperometry. The results indicated that the linear range, detection limit. and response slope of biosensor was 2.00×10^-4-1.57×10^-3 mol·L^-1, 2.0×10^-4 mol·L^-1 and 5.06×10^5 nA·mol^- 1·L, respectively.     

Synthesis, structures and some reactions of Ru(CCCCFc)(PP)Cp (PP = dppm, dppe) and related compounds

The compounds Ru(CCCCFc)(PP)Cp [PP = dppe (1), dppm (2)], have been obtained from reactions between RuCl(PP)Cp and FcCCCCSiMe₃ in the presence of KF (1) or HCCCCFc and K[PF₆] (2), both with added dbu. The dppe complex reacts with Co₂(CO)₆(L₂) [L₂ = (CO)₂, dppm] to give 3, 4 in which the Co₂(CO)₄(L₂) group is attached to the outer CC triple bond. The PPh₃ analogue of 3 (5) has also been characterised. In contrast, tetracyanoethene reacts to give two isomeric complexes 6 and 7, in which the cyano-olefin has added to either CC triple bond. The reaction of RuCl(dppe)Cp with HCCCCFc, carried out in a thf/NEt₃ mixture in the presence of Na[BPh₄], gave [Ru{CCC(NEt₃)CHFc}(dppe)Cp]BPh₄ (8), probably formed by addition of the amine to an (unobserved) intermediate butatrienylidene [Ru(CCCCHFc)(dppe)Cp]⁺. The reaction of I₂ with 8 proceeds via an unusual migration of the alkynyl group to the Cp ring to give [RuI(dppe){η-C₅H₄CCC(NEt₃)CHFc}]I₃ (9). Single-crystal X-ray structural determinations of 1, 2 and 4-9 are reported.     

Synthesis and characterization of functionalized ferrocenylsilanes bearing a bulky substituent

Several types of overcrowded ferrocenylsilanes, Tbt(Fc)SiX₂(Tbt=2, 4, 6-tris[bis(trimethylsilyl)methyl]phenyl, Fc=ferrocenyl, X = H, OH, and Br) were synthesized and characterized. In addition, DFT calculations for ferrocenylsilanediol systems indicated the existence of the intramolecular hydrogen bonding between the Fe atom and H–O moiety in Tbt(Fc)Si(OH)₂. Dedicated to Professor Mitsuo Kira on the occasion of his 2005 Wacker Awardy     

一个含二茂铁基的镉配合物Cd(dppf)I2的合成和表征

The complex containing ferroceneyl, Cd(dppf)I₂(dppf=1,1-bis(diphenylphosphino) ferrocene), was syn-thesized and characterized by IR, Uv-vis DRIS spectrum and X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, a=37.439(3)?, b=10.2472(6)?, c=18.719(1)?, β=110.4715(16)°, V=6727.8(8)?³, Z=8, D_c=1.818g·cm^-3, F(000)=3536, μ=3.015mm^-1, R=0.0308, wR=0.0692. dppf coor-dinates to Cd(Ⅱ) as bidentate ligand, and the coordination environment of Cd(Ⅱ) is a distorted tetrahedron. The electronic structures of Cd(dppf)I₂ and Cd(dppf)Br₂ are discussed by quantum chemistry calculation.     

芳茂铁四氟硼酸盐的制备

以二茂铁为原料制备了多种阳离子光引发剂芳茂铁四氟硼酸盐，其中包括两种新物质，即两种带乙酰基的芳茂铁四氟硼酸盐，分别为 [环戊二烯基-铁-(2 ,5-二甲基苯乙酮 )]四氟硼酸盐和 [(乙酰基-环戊二烯基 )-铁-对二甲苯]四氟硼酸盐。另外，本文考察了此配体交换反应的反应条件对反应收率的影响，并成功找到了芳茂铁四氟硼酸盐的提纯方法。     

含二茂铁基的氨基硫脲均三唑和恶二唑的合成

以二茂铁为原料，经过多步反应合成了16个二茂铁的衍生物，其中13个为新化合物，这些化合物经元素分析，红外光谱，核磁共振氢谱和质谱等对其结构进行了表征，除化合物3－二茂铁基二硫代肼基甲酸钾外，其余在水中均溶解性差，在丙酮，乙醇等中有一定溶解度，均易溶于DMF和DMSO。