四(4－N-吡啶基)卟啉衍生物的合成及表征

阳离子卟啉配体;配合物;还原电位;四(4－N-吡啶基)卟啉衍生物的合成及表征     

Kinetic parameters of the electroreduction of oxygen on a graphitized carbon electrode activated by tetrakis(4-methoxyphenyl)porphyrin and its cobalt complexes

Electrochemical and electrocatalytic properties of tetrakis(4-methoxyphenyl)porphyrin, tetrakis(4-methoxyphenyl)porphyrinatocobalt(II), and (tetrakis(4-methoxyphenyl)porphyrinato)chlorocobalt(III) are studied using the method of cyclic voltammetry. The redox-potentials of the electrode processes, the potentials of the half-wave and stationary rate constants for electroreduction of molecular oxygen are determined from an analysis of the voltammetric curves. The cobalt complex is found to be characterized by higher electrocatalytic activity than other analyzed compounds.     

Studies in the tetraarylborates : Part VII. The preparation and reagent properties of some new nitrogen heterocyclic tetraarylboraees — especially sodium tetrakis(l-imidazolyl) borate,a novel gravimetric reagent for hydrogen ion

Three new tetraarylborates containing nitrogen heterocycles have been synthesized. Sodium tetrakis(1-imidazolyl)borate and sodium tetrakis(1-benzimidazolyl)borate were prepared in very high yield by syntheses which were easy to perform in situ. Interesting analytical properties which are very different from the carbocyclic tetraarylborates were noted in both compounds. Precipitate formation oftetrakis(1-imidazolyl)borate with hydrogen and divalent cations was observed. The feasibility of determination of the hydrogen cation by tetrakis(1-imidazolyl)borate was demonstrated.     

Pincer-porphyrin hybrids

[reaction: see text] Starting from tetrakis(3,5-bis(bromomethyl)phenyl)porphyrin, pincer-porphyrin hybrid molecules (tetrakis(ECE-pincer)porphyrin; E = N, P, S) based on a tetraphenylporphyrin skeleton have been prepared in high yields. These multi-ligand site compounds could be selectively metalated at their peripheries, which was shown by X-ray crystallography.     

Reactions of hexafluorobenzene with some organometallic reagents

The inverse addition of trichloro-2-thienyl-lithium to hexafluorobenzene in THF or ether has given 1,4-bis(trichloro-2-thienyl) tetrafluorobenzene in addition to the tetrakis(trichloro-2-thienyl)difluorobenzene. n-Butyl-lithium with hexafluorobenzene gave mono, bis tris and tetrakis compounds whereas t-BuLi afforded only 1,4-bis(t-butyl)tetrafluorobenzene in excellent yield. Other organolithium and organomagnesium reagents gave the expected products. IR, ¹⁹F NMR and UV spectral data are presented for the several new compounds.     

meso-四(对烷氧苯基)卟啉及其金属配合物的合成、表征及液 晶性

合成了meso-四(对烷氧苯基)卟啉及其Cu,Co,Zn,Pb金属配合物38个,其中14个为未见文献报道的新化合物。用元素分析,IR,UV,^1HNMR,MS对其进行了表征,确证了其结构。研究了这五个系列化合物的液晶性能,发现16个化合物具有液晶性,探讨了烷氧基链长及配位金属离子对液晶性能的影响。     

Synthesis,molecular structure,and vibrational spectra of tetrakis(2-hydroxyethylammonium) chloride and its triethanolamine precursor and metabolite

A unique one-stage synthesis of tetrakis(2-hydroxyethylammonium) salts, precursors of new hypervalent silicon compounds, has been developed. The vibration spectra of tetrakis(2-hydroxyethylammonium) chloride and its triethanolamine precursor and metabolite have been studied by IR spectroscopy and quantum chemistry. Analysis of alterations in the modes with increasing number of HOCH₂CH₂ groups has been performed.     

Tetrakis(dimethoxyphenyl)adamantane (TDA) and Its Inclusion Complexes in the Crystalline State: A Versatile Carrier for Small Molecules

Molecular storage solutions for incorporating small molecules in crystalline matrices are of interest in the context of structure elucidation, decontamination, and slow release of active ingredients. Here we report the syntheses of 1,3,5,7‐tetrakis(2,4‐dimethoxyphenyl)adamantane, 1,3,5,7‐tetrakis(4‐methoxyphenyl)adamantane, 1,3,5,7‐tetrakis(4‐methoxy‐2‐methylphenyl)adamantane, and 1,3,5,7‐tetrakis(4‐methoxy‐2‐ethylphenyl)adamantane, together with their X‐ray crystal structures. All four compounds crystallize readily. Only the octaether shows an unusual level of (pseudo)polymorphism in its crystalline state, combined with the ability to include a number of different small molecules in its crystal lattices. A total of 20 different inclusion complexes with guest molecules as different as ethanol or trifluorobenzene were found. For nitromethane and benzene, schemes for uptake and release are presented.     

Reductive dehalogenation of α-halogenated carbonyl and cyano compounds with the hexamethyldisilane/tetrakis(triphenylphosphine)palladium system

Treatment of α-halogenated carbonyl or cyano compounds with hexamethyldisilane in the presence of catalytic amounts of tetrakis(triphenylphosphine)-palladium gives the corresponding parent carbonyl or cyano compounds in excellent yields via oxy-π-allyl(trimethylsilyl)palladium intermediates.     

Synthesis and properties of tetrazole-containing oligomers

Linear, star-shaped, and hyperbranched oligomeric compounds containing tetrazole cycles in the main chains are synthesized via the polycondensation (polyalkylation) of N-H unsubstituted bis(tetrazoles), tris(tetrazoles), and tetrakis(tetrazoles) with compounds containing mobile halogen atoms. Some properties of the oligomers are studied. Some of the oligomers are characterized by high density and a large content of nitrogen.     

四(ω-羟基聚乙氧基)-季戊四醇醚及其磺酸酯化合物的合成

报道了Cascade(树状分枝化合物)分子四方向核心四-(ω-羟基聚乙氧基)-季戊四醇醚及四-(ω-对甲苯磺酰氧聚乙氧基)-季戊四醇醚的合成,其结构经元素分析、IR、NMR和MS图谱确证。     

Metal Carbonyl Spectra : by P.S. Braterman,Academic Press,London/New York/San Francisco, 1975, vii + 286 pages, $22.25.

Vinyl halides react with alkyllithium compounds in the presence of tetrakis(triphenylphosphine)palladium to give olefins stereospecifically in excellent or fairly good yields. When less reactive Grignard reagents are employed instead of alkyllithium compounds, these reactions can be carried out catalytically with palladium.     

Tetrakis(imidazolyl)borate-based coordination polymers: group II network solids,M[B(Im)4]2(H2O)2 (M = Mg,Ca, Sr)

We are using the coordinating anion tetrakis(imidazolyl)borate to construct new metal-organic framework structures. In this report, we present three alkaline earth metal network solids incorporating this anion. All three compounds have the same formula, M[B(Im)(4)](2)(H(2)O)(2) (M = Mg, Ca, Sr), and the same coordination environment about the metal. However, the three compounds have different network structures with different degrees of hydrogen bonding; the Mg material forms a two-dimensional network and the Ca and Sr compounds form one-dimensional chains. In addition, we present the structure of the protonated anion B(HIm)(Im)(3) as a model for the default structure of this anion and discuss how the conformation of tetrakis(imidazolyl)borate can affect the structure of network solids.     

Synthesis of fluorine analogs of protoporphyrin potentially useful for diagnosis and therapy of cancer. IV. Synthesis of (trifluorovinyl)vinyl- and (1-chloro-2,2-difluorovinyl)vinyldeuteroporphyrins.

Trifluoro or chlorodifluoro analogs of protoporphyrin, the compounds in the title, were synthesized for use in the diagnosis and therapy of cancer. 3- Or 8-acetyldeuteroporphyrin dimethyl esters (2 and 3) were iodinated with iodine in the presence of potassium carbonate to the corresponding iodo compounds (5 and 6). The iodo compounds (5 and 6) were treated with bis(trifluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)-palladium to give trifluorovinyl derivatives (7 and 8) in good yields. Reduction of the acetyl group of 7 and 8 with sodium borohydride afforded the corresponding hydroxyethyl derivatives (9 and 10). Compounds (9 and 10) were dehydrated with methanesulfonyl chloride and triethylamine to give (trifluorovinyl)vinyldeuteroporphyrin dimethyl esters (11 and 12). Treatment of 5 and 6 with bis(1-chloro-2,2-difluorovinyl)zinc in the presence of tetrakis(triphenylphosphine)palladium, followed by similar reactions as above gave (1-chloro-2,2-difluorovinyl)-vinyldeuteroporphyrin dimethyl esters (17 and 18).     

Investigation of the SERS behaviour of porphyrins with different surface concentrations on electrochemically prepared Ag-surface

Surface-enhanced Raman scattering (SERS) spectra, taken with 632.8 nm excitation are reported for the water-soluble tetrakis(3-N-methylpyridyl)porphyrin chloride (TMPyP(3)), tetrakis(4-N-methylpyridyl)porphyrin chloride (TMPyP(4)) and Sn(IV)tetrakis(4-N-methylpyridyl)porphyrin chloride (Sn(IV)TMPyP(4)) using an electrochemically prepared Ag surface with an area ca. 12.56 mm2. It was found that the spectra vary as increasing amounts of the compounds are placed on the surface, with surface concentrations in the approximate range 1000-5 pmol/12.56 mm2. We suggest that the reasons for the changes be that the reaction means between porphyrin molecules and Ag surface is different and the porphyrin macrocyclic molecules adopt different orientation as the surface concentrations decrease.     

NO2 gas detection by Langmuir-Blodgett films of copper phthalocyanine multilayer structures

Copper (II) phthalocyanine derivatives with four alkyl chains were synthesized. Langmuir-Blodgett (LB) films of the following two compounds were deposited: Cu(II)[tetrakis(3,3-dimethyl-butoxycarbonyl)] phthalocyanine and Cu(II)[tetrakis(n-butoxycarbonyl)] phthalocyanine. Moreover, LB films from a 1:1 mixture of the two compounds were prepared. All isotherms and optical data were consistent with the molecules being stacked nearly edge-on to the substrate, with the molecular faces having a preferred orientation perpendicular to the dipping direction. The dynamic response characteristics of the electrical conductance of the LB films to different NO₂ concentrations in dry air are described. A relationship has been observed between the anisotropic molecular orientation and the electrical conductivity parallel to the substrate.     

On the reported mesomorphism of lanthanide complexes containing the hemicyanine structural unit

Close examination of the thermal behaviour of the (E)-N-hexadecyl-4-N', N'-dimethylaminostilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato)lanthanide(III) complexes has revealed that these compounds are not mesomorphic, in contradiction to an earlier report in the literature (K. Z. Wang et al., 1995, Solid State Commun. 95, 223). By replacing the bromide of the hemicyanine precursor (see the scheme) by a tetrakis(beta-diketonato)lanthanide(III) anion, new complexes were synthesized, but none shows a mesophase. Reasons for the absence of mesomorphism are discussed. Transition temperatures for the mesomorphic hemicyanine bromides are reported.     

Cyclobutadiene dianions consisting of heavier group 14 elements: synthesis and characterization

The first "heavy" cyclobutadiene dianions (CBD2-), tetrakis(di-tert-butylmethylsilyl)-1,2-disila-3,4-digermacyclobutadiene dianion 22- and tetrakis(di-tert-butylmethylsilyl)tetrasilacyclobutadiene dianion 42-, have been synthesized by the reductive dehalogenation of the corresponding precursors with potassium graphite in THF. Structural characterization of [K+(thf)2]2.22- and [K+(thf)2]2.42- has been achieved by X-ray crystallography, showing that the central four-membered ring is significantly folded and has two eta2-1,3-coordinated potassium cations accommodated above and below the ring. The "heavy" CBD2-'s 22- and 42- were found to be nonaromatic compounds, a conclusion that was supported by nucleus-independent chemical shift (NICS) calculations showing a lack of diatropic ring current effects.     

Tetrakis(imidazolium) macrocyclic receptors for anion binding

New (tetrakis)imidazolium macrocyclic receptor systems of variable cavity size have been synthesised by stepwise alkylation reactions of bis(imidazolium) precursor compounds. Proton NMR titration studies reveal the macrocycles to strongly bind halide and benzoate anions, with two receptor systems displaying notable selectivity for fluoride in competitive acetonitrile-water (9:1) solvent media.     

Volatile beta-ketoiminato- and beta-diketiminato-based zirconium complexes as potential MOCVD precursors

An amine elimination pathway has been used to produce a number of homo- and heteroleptic zirconium complexes, starting from tetrakis(dialkylamido)zirconium complexes and beta-diketimine or, alternatively, Schiff Base compounds. Reaction of 2 equiv of the bidentate beta-diketimine (2Z,4E)-N-methyl-4-(methylimino)pent-2-en-2-amine with Zr(NR(2))(4) (R = Me, Et) affords the six-coordinate heteroleptic compounds bis(N-methyl-4-(methylimino)pent-2-en-2-amido)bis(dialkylamido)zirconium 1 (alkyl = Me) and 2 (alkyl = Et). The dynamic behavior of these two compounds in solution has been investigated. Reaction with the isopropyl-substituted beta-diketimine (2Z)-N-isopropyl-4-(isopropylimino)pent-2-en-2-amine gives the five-coordinate mono(diketiminato)-substituted compound (N-isopropyl-4-(isoropylimino)pent-2-en-2-amido)tris(dimethylamido )zirconium, 3. With employment of the Schiff base (3Z)-4-(methylamino)pent-3-en-2-one, it was also possible to prepare the six-coordinate bis(4-(methylamino)pent-3-en-2-onato)bis(diethylamido)zirconium compound 4. When the bidentate ligand bearing hydrogen as substituent on the imino-nitrogen atom was employed, homoleptic tetrakis(beta-ketoiminato)- and tetrakis(beta-diketiminato)zirconium compounds 5 and 6 can be obtained. Complexes 1 and 5 have been tested for their air stability with reference to Zr(NMe(2))(4). The stability order turned out to be 1 > 5 > Zr(NMe(2))(4). The thermal properties and volatility of all the compounds are discussed in view of their potential application in metal-organic chemical vapor deposition processes (MOCVD) of zirconium nitride.