[Fe(N2H5)2(SO4)2]n的合成、结构和磁性质

采用水热合成方法得到一例新的过渡金属铁(Fe)的含肼硫酸盐: [Fe(N₂H₅)₂(SO₄)₂]_n (1). 用单晶X射线衍射的方法对其晶体结构进行了表征. 结果表明, 该化合物以硫酸根为桥连配体, 质子化的肼分子为端基配体, 形成一维(1D)链状结构. 肼分子和硫酸根形成的链间氢键, 将1D链进一步扩展成三维(3D)结构. 磁性测试表明化合物在低温下显示出反铁磁有序的磁行为.     

Silylhydrazine und dimere N,N′‐Dilithium‐N,N′‐bis(silyl)hydrazide – Synthesen,Reaktionen, Isomerisierungen

Silylhydrazines and Dimeric N,N′‐Dilithium‐N,N′‐bis(silyl)hydrazides – Syntheses, Reactions, Isomerisations Di‐tert.‐butylchlorosilane reacts with dilithiated hydrazine in a molar ratio to give the N,N′‐bis(silyl)hydrazine, [(Me₃C)₂SiHNH]₂, ( 5 ). Isomeric tris(silyl)hydrazines, N‐difluorophenylsilyl‐N′,N′‐bis(dimethylphenylsilyl)hydrazine ( 7 ) and N‐difluorophenylsilyl‐N,N′‐bis(dimethylphenylsilyl)hydrazine ( 8 ) are formed in the reaction of N‐lithium‐N′‐N′‐bis(dimethylphenylsilyl)hydrazide and F₃SiPh. Isomeric bis(silyl)hydrazines, (Me₃C)₂SiFNHNHSiMe₂Ph ( 9 ) and (Me₃C)₂‐ SiF(PhMe₂Si)N–NH₂ ( 10 ) are the result of the reaction of di‐tert.‐butylfluorosilylhydrazine and ClSiMe₂Ph in the presence of Et₃N. Quantum chemical calculations for model compounds demonstrate the dyotropic course of the rearrangement. The monolithium derivative of 5 forms a N‐lithium‐N′,N′‐bis(silyl)hydrazide ( 11 ). The dilithium salts of 5 ( 13 ) and of the bis(tert.‐butyldiphenylsilyl)hydrazine ( 12 ) crystallize as dimers with formation of a central Li₄N₄ unit. The formation of 12 from 11 occurs via a N′ → N‐silyl group migration. Results of crystal structure analyses are reported.     

The directional reaction of hydrazine with silver complexes. Part 3. Synthesis and characterization of a copper(I)-hydrazine intermediate complex,Na(N2H4)CuCl2

On the basis of previous work on the directional reaction of hydrazine with silver complexes, the Na(N₂H₄)CuCl₂ complex was prepared in NaOH solution and its structure determined by elemental analysis, electronic, e.s.r., i.r. spectra and by d.t.a. analysis. The i.r. spectrum indicated the presence of bridging hydrazine and chloride. The complex may be polymeric, i.e. an axially elongated (4 + 2) octahedron, with a layer structure connected by hydrazine and chloride ions. Na⁺ ions are also present in the layers. The addition of the Na(N₂H₄)CuCl₂ complex to N₂H₄ plus the Ag(NH₃)₂ ⁺ cation not only enhances the oxidation rate, but also increases the N₂(%) formed by four-electron reduction of hydrazine by the silver complex.     

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.     

三个双肼桥连金属配合物的合成,结构和磁性

采用水热合成方法得到3个新的双肼桥连过渡金属化合物：[M（N₂H₄）₂Cl₂]_n（M=Mn（1）,Ni（2））,{[Co_1.5（N₂H₄）₃PO₄（H₂O）]·H₂O}_n（3）,用单晶X射线衍射方法对其晶体结构进行表征。化合物1是以2个肼分子桥联金属Mn和Ni形成1D链状结构,而粉末XRD显示1与2是同构的。化合物3是以2个肼分子桥联金属Co形成1D链,不同的1D链再通过磷酸根PO₄^3-进一步堆积形成3D结构。磁性测试表明肼桥在磁性中心之间传递反铁磁耦合作用。     

Die Umsetzung von Dialkylaluminiumchloriden mit Bis(trimethylsilyl)hydrazin: Bildung von Addukten R2AlCl · NH2NHSiMe3 mit dem thermisch unbeständigen Trimethylsilylhydrazin

The Reaction of Dialkylaluminium Chlorides with Bis(trimethylsilyl)hydrazine: Formation of the Adducts R₂AlCl · NH₂NHSiMe₃ Containing the Unstable Monotrimethylsilylhydrazine Bis(trimethylsilyl)hydrazine did not react with dialkylaluminium chlorides R₂AlCl [R = CH₂CMe₃, CMe₃ and CH(SiMe₃)₂] by the formation of trimethylchlorosilane, but by dismutation to yield tris(trimethylsilyl)hydrazine and trimethylsilylhydrazine. The unstable, sterically less shielded NH₂NHSiMe₃ was stabilized by the coordination to the coordinatively unsaturated aluminium compounds. The adducts R₂AlCl · NH₂NHSiMe₃ were formed, which were characterized by crystal structure determinations with R = CMe₃ and CH(SiMe₃)₂. In all cases, the hydrazine derivative binds to the aluminium atoms via the more basic NH₂ nitrogen atom. The adduct Me₃CAlCl₂ · NH₂N(SiMe₃)₂ containing intact 1,1‐bis(trimethylsilyl)hydrazine as a ligand was isolated in a trace amount and also characterized by a crystal structure determination.     

Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n=3, 4, 5 and 6)

Hydrazinium 2,n-pyridinedicarboxylates of general compositions N₂H₅HA, (N₂H₅)₂A·H₂O and N₂H₅HA·H₂A, where H ₂ A=2,n-pyridinedicarboxylic acid (n=3, quinolinic acid;n=4, lutidinic acid; n=5, isocinchomeronic acid and n=6, dipicolinic acid) have been prepared by the neutralisation of aqueous solution of hydrazine hydrate with the respective acids, in stoichiometric ratios. Formation of these hydrazinium derivatives has been confirmed by analytical, IR spectral and thermal studies. Among these, the monohydrazinium salts are anhydrous whereas the dihydrazinium salts are monohydrated. While lutidinic and dipicolinic acids form all the three types of salts, the quinolinic and isocinchomeronic acids do not form N₂H₅HA·H₂A and N₂H₅HA, respectively, except the other two types. Infrared spectra of these salts reveal N-N stretching frequencies of the hydrazinium ion in the region 970-950 cm^-1. The simultaneous TG and DTA of these salts show that all of them decompose without clear melting and lose hydrazine endothermically between 200 and 280°C, except dihydrazinium isocinchomeronate monohydrate in which half of the hydrazine molecule is lost exothermically, to give pyridinemono- or dicarboxylic acid intermediate which further decomposes exothermically to gaseous products. This revised version was published online in August 2006 with corrections to the Cover Date.     

Beiträge zur Chemie des Hydrazins und seiner Derivate. XVII. Darstellung und Eigenschaften von Barium-, Strontium- und Calciumhydrazid

Barium, strontium and calcium hydrazide have been synthesised and characterised for the first time from the corresponding pernitrides Me₃N₄ (Me = Ba, Sr, Ca) and anhydrous hydrazine. Analytical and IR-spectroscopic studies show that these hydrazides have the composition Me(N? NH₂). Bariumhydrazile has also been obtained from barium or barium amide and anhydrous hydrazine, and strontium hydrazide from strontium and anhydrous hydrazine.     

三个双肼桥连金属配合物的合成,结构和磁性

采用水热合成方法得到3个新的双肼桥连过渡金属化合物：[M（N₂H₄）₂Cl₂]_n（M=Mn（1）,Ni（2））,{[Co_1.5（N₂H₄）₃PO₄（H₂O）]·H₂O}_n（3）,用单晶X射线衍射方法对其晶体结构进行表征。化合物1是以2个肼分子桥联金属Mn和Ni形成1D链状结构,而粉末XRD显示1与2是同构的。化合物3是以2个肼分子桥联金属Co形成1D链,不同的1D链再通过磷酸根PO₄^3-进一步堆积形成3D结构。磁性测试表明肼桥在磁性中心之间传递反铁磁耦合作用。     

Photoelectrochemical oxidation of hydrazine on TiO2 modified titanium electrode: its application for detection of hydrazine

Despite extensive investigations on the photoelectrochemical properties of TiO₂-based electrodes, it is surprising that no photoelectrochemical investigation has been done for the case of hydrazine oxidation. In this paper, TiO₂ modified titanium (Ti/TiO₂) electrode was fabricated by anodization process under a constant applied potential. The morphological and microstructural characterization of the Ti/TiO₂ electrode was performed by scanning electron microscopy (SEM). The electrochemical and photoelectrochemical behavior of Ti/TiO₂ electrode in the absence and presence of hydrazine was examined by cyclic voltammetry and linear sweep voltammetry. Experimental results indicated that the photocurrent response of photoelectrode was highly increased in the presence of hydrazine especially at lower potentials. It can be due to hole scavenging effect of hydrazine which decreases the recombination of photogenerated electrons and holes. Based on these perceptions, a simple photoelectrochemical sensor for detection of hydrazine was obtained. The sensor showed high reproducibility, stability, and selectivity properties. This photoelectrode was successfully applied for direct determination of hydrazine in tap water.     

Synthesis, characterisation and thermal analysis of copper (II) and chromium (II, III) hydrazine carboxylates

Copper(II) hydrazine carboxylate monohydrate, Cu(N₂H₃COO)₂·H₂O and chromium (II, III) hydrazine carboxylate hydrates, Cu(N₂H₃COO)₂·H₂O and Cu(N₂H₃COO)₂·3H₂O have been prepared and characterised by chemical analysis, IR, visible spectra and magnetic measurements. Thermal analysis of the copper complex yields a mixture of copper metal and copper oxide. Chromium complexes on thermal decomposition yield Cr₂O₃ as residue. Decomposition of chromium(HI) complex under hydrothermal conditions yield CrOOH, a precursor to CrO₂.     

From 1D to 2D Cd(II) and Zn(II) Coordination Networks by Replacing Monocarboxylate with Dicarboxylates in Partnership with Azine Ligands: Synthesis,Crystal Structures,Inclusion, and Emission Properties

Eight mixed-ligand coordination networks, [Cd(2-aba)(NO₃)(4-bphz)_3/2]_n·n(dmf) (1), [Cd(2-aba)₂(4-bphz)]_n·0.75n(dmf) (2), [Cd(seb)(4-bphz)]_n·n(H₂O) (3), [Cd(seb)(4-bpmhz)]_n·n(H₂O) (4), [Cd(hpa)(3-bphz)]_n (5), [Zn(1,3-bdc)(3-bpmhz)]_n·n(MeOH) (6), [Cd(1,3-bdc)(3-bpmhz)]_n ·0.5n(H₂O)·0.5n(EtOH) (7), and [Cd(NO₃)₂(3-bphz)(bpe)]_n·n(3-bphz) (8) were obtained by interplay of cadmium nitrate tetrahydrate or zinc nitrate hexahydrate with 2-aminobenzenecarboxylic acid (H(2-aba)), three dicarboxylic acids, sebacic (decanedioic acid, H₂seb), homophthalic (2-(carboxymethyl)benzoic acid, H₂hpa), isophthalic (1,3-benzenedicarboxylic acid, H₂(1,3-bdc)) acids, bis(4-pyridyl)ethane (bpe) and with four azine ligands, 1,2-bis(pyridin-4-ylmethylene)hydrazine (4-bphz), 1,2-bis(1-(pyridin-4-yl)ethylidene) hydrazine (4-bpmhz), 1,2-bis(pyridin-3-ylmethylene)hydrazine (3-bphz), and 1,2-bis(1-(pyridin-3-yl) ethylidene)hydrazine (3-bpmhz). Compounds 1 and 2 are 1D coordination polymers, while compounds 3–8 are 2D coordination polymers. All compounds were characterized by spectroscopic and X-ray diffraction methods of analysis. The solvent uptakes and stabilities to the guest evacuation were studied and compared for 1D and 2D coordination networks. The de-solvated forms revealed a significant increase of emission in comparison with the as-synthesized crystals.     

A highly stable nano γ-Fe2O3/gold-film modified electrode for electrochemically sensitive sensing to hydrazine

The magnetic γ-Fe₂O₃ material was prepared in a new way and characterized by transmission electron microscopy and X-ray diffraction. It was modified on a glass carbon electrode (GCE) coated with gold film to form nano γ-Fe₂O₃/Au/GCE. The electrooxidation of hydrazine has been deeply explored with the resulting electrode in 0.1 M phosphate-buffered saline (pH 7.0). The affecting factors containing pH of supporting electrolyte, scan rate, deposition time, amount of γ-Fe₂O₃, and possible interferences were investigated, and the oxidation mechanisms of hydrazine on the γ-Fe₂O₃/Au/GCE were also explored. The amperometric response to hydrazine is linear in the range of 0.02 to 11 μM, and the detection limit is 6 nM at a SNR of 3. The prepared sensor exhibited good sensitivity, stability, and lower detection limit for the determination of hydrazine injection.     

Über 1, 5-Diphenyl-2, 3, 6, 7-tetrahydro-1H, 5H-pyrazolo[1, 2-a]pyrazole(2, 6-Diphenyl-1, 5-diazabicyclo[3, 3, 0]octane)

The synthesis of a 1, 5-diphenyl perhydro-pyrazolo-[1, 2-a] pyrazole (IV) (m. p. = 170–171°) by LiAlH₄-reduction of its 3, 7-dioxo derivative Va, one of the stereoisomers of V, is described. Va was obtained in small yield by the reaction of cinnamic acid with its hydrazide or with hydrazine. It proved to be identical with the compound obtained previously by interaction of cinnamic acid hydrazide with iodine which in the literature erroneously had been described as N, N′-dicinnamoyl hydrazine. This hydrazine now was obtained by bis-acylation of hydrazine with cinnamoyl chloride. In Va the extremely low NMR. absorption of the tertiary protons at ρ = 4,6 ppm is probably due to the spatial grouping with the proton situated in the deshielding region of the carbonyl group. Previously, another tertiary proton with a very low NMR. absorption at ρ = 4,85 ppm has been observed in the «bisimide M», the main criss-cross addition product of one mole benzaldazine and two moles of N-(n-butyl)-maleinimide. A stereostructure for bisimide M is now proposed, which is a hybrid between those of the bisimides L and H.     

A Novel Chemical Sensor Based on Sb2S3 Film for Highly Sensitive Detection of Hydrazine

The Sb₂S₃ film on indium‐tin oxide (ITO) substrate has been used as an efficient electron transfer mediator for the fabrication of novel chemical sensor towards hydrazine, which is a diamine known as neurotoxin and carcinogen. Sb₂S₃ film is deposited on ITO substrate by drop‐casting process using Sb₂S₃ solution as precursor and possesses reticular structure with the morphology of uniform hollow hemispheres. The fabricated chemical sensor for selective detection of hydrazine displays a high sensitivity of 106.25 μA/(mM cm²) with a low detection limit of 0.5 μM and it also exhibits excellent reproducibility and stability in hydrazine detection.     

Room-Temperature Synthesis of Copper and Silver, Nanocrystalline Chalcogenides in Mixed Solvents

Copper and silver nanocrystalline chalcogenides, Cu_2−xSe, Cu₂Te, Ag₂Se, and Ag₂Te, have been successfully synthesized in a mixture of ethylenediamine and hydrazine hydrate as a solvent at room temperature. Products showed different morphologies, such as nanotubes, nanorods, and nanoparticles. The results indicated that the coordination and chelation abilities of ethylenediamine play an important role in the formation of one-dimensional nanocrystalline binary chalcogenides, and hydrazine hydrate is crucial to the electron transfer in the room temperature reactions. These transition-metal nanocrystalline chalcogenides as prepared were analyzed by X-ray powder diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The UV-Vis absorption properties of these nanocrystals were also measured.     

The low temperature synthesis of metal oxides by novel hydrazine method

The hydroxide, oxalate and citrate precursors of the metal oxides such as γ-Fe₂O₃, (MnZn)Fe₂O₄, Cu(K)Fe₂O₄, BaTiO₃, La(Sr)MnO₃, La(Sr)AlO₃, La/Gd(Ca/Ba/Sr)CoO₃, and anatase TiO₂ on modifications with the hydrazine decompose at low temperatures give single phase oxides of superior properties, while the complexes without such modification require higher temperatures for achieving the phases. The hydrazine released at lower temperatures reacts with the oxygen in the atmosphere, N₂H₄+O₂→N₂+2H₂O; ΔH=−625 kJ mol⁻¹, and liberates enormous energy that is sufficient for the oxidative decomposition of the complexes now devoid of hydrazine. Such extra energy is not available in the case of the precursors without such modifications. The reaction products of hydrazine oxidation provide desired partial pressure of moisture needed for the stabilization of γ-Fe₂O₃. Also, the nitrogen that is formed in the reaction of hydrazine with oxygen gets trapped in the lattice of TiO₂ giving yellow color nitrogen doped TiO_2−xN_x photocatalyst. Thus, hydrazine method of preparation has many advantages in the preparation of metal oxides of superior properties.     

新型钛基镍电极对肼氧化反应的电催化活性

A novel titanium-supported nickel electrode(Ni/Ti) was fabricated by a hydrothermal process using NiSO4 and hydrazine as raw materials. The structure of Ni/Ti was characterized by SEM and EDS. Oxidation of hydrazine on the Ni/Ti electrode in 1 mol·L-1 NaOH solution was studied with cyclic voltammograms(CV) and chronoamperometry (CA).The results show that Ni/Ti electrode was electrochemically active towards hydrazine oxidation. The high current density was recorded on the Ni/Ti electrode,and the onset potential for the hydrazine oxidation was-0.3 V as the hydrazine concentration was 70 mmol·L-1. This novel nickel electrode would be a promising anodic material used in direct hydrazine fuel cells.     

Novel route to the synthesis of chalcogenolanes, chalcogenanes, and 1,2-dichalcogenaepanes*

The saturated heterocyclic compounds C₄H₈Y, C₅H₁₀Y, and C₅H₁₀Y₂ (Y = Se or Te) have been prepared by the reaction of 1,4-dibromobutane or 1,5-dibromopentane with potassium chalcogenides. The novelty of the route consists of the use of the hydrazine hydrate–KOH system for the reductive generation of potassium selenide, telluride, diselenide or ditelluride from elemental chalcogens.     

Cooperative Ni(Co)-Ru-P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self-powered H2 Production

Water electrolysis for H₂ production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru₁−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm⁻², respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm⁻² at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru₁−NiCoP optimize H* adsorption, and enhance adsorption of *N₂H₂ to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H₂ production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h⁻¹ m⁻².