螯合物(FcCOCHCOCH3)2Cu与(FcCOCHCOCH3)3Fe的合成及其燃烧催化活性

含有铁、铬、铜等过渡元素的一些化合物,如铁的氧化物、铜的亚铬酸盐、二茂铁及其衍生物等都可作为复合固体推进剂的燃速催化剂.在二茂铁衍生物中主要是烷基衍生物,如叔丁基二茂铁、正辛基二茂铁、γ-二茂铁丁酸丁酯以及1,7-二(二茂铁基)庚烷、2,2-双(乙基二茂铁基)丙烷等.上述催化剂的变化趋势是由单二茂铁基向双二茂铁基发展,     

双(烷基二茂铁基)丙烷的合成及其燃速催化性质

双(烷基二茂铁基)丙烷的合成及其燃速催化性质;二茂铁衍生物;燃速催化剂     

新型燃速催化剂—烷基二茂铁桥联双聚分子的电化学研究

液态烷基二茂铁桥联双聚分子是一类新型燃速催化剂,它不仅具有催化活性高的优良特性,而且挥发性及迁移性均有改善,适宜用于火箭燃料复合固体推进剂。本文合成9种含不同取代基的双核二茂铁化合物,其中6种为首次合成。该9种化合物的通式为:其结构通式、各化合物的编号、英文名缩写及所含取代基和桥联基表示如下:     

双二茂铁基烷酰化衍生物的还原反应

二茂铁甲烷,2,2-双二茂铁丙烷,2,2-双二茂铁基丁烷,2,2-双二茂铁基戊烷与乙酸酐、丙酸酐、正丁酸酐通过傅氏酰基化反应生成一系列双二茂铁基烷的酰化衍生物,再经LiAlH_4还原得到318个相应的α-羟基双二茂铁烷衍生物。文中并对它们的红外光谱和~1H NMR谱性质进行了研究。     

2-单核和双核茂铁基-1,3-二烷基苯并咪唑盐的合成、结构及性质研究

以2-二茂铁基苯并咪唑(2)为原料,合成了1-甲基-2-二茂铁基-3-乙基苯并咪唑碘盐(4)和六氟磷酸盐(5);甲酰化的2,2-双二茂铁基丙烷(6)与邻苯二胺在甲醇作溶剂,回流,碘催化下反应,得到2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]苯并咪唑(7),以7为原料合成了1-甲基-2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]-3-乙基苯并咪唑碘盐(9)和六氟磷酸盐(10).电化学分析表明所得的盐化合物中,与苯并咪唑阳离子直接相连的二茂铁的氧化电位相对2和7均产生了较大正移.对化合物4的单晶结构进行了解析,晶体结构中存在π-π堆积.UV-Vis吸收光谱表明所得盐化合物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)测试表明碘盐4对高氯酸铵(AP)热分解有较好催化效果.     

二茂铁-噻吩和联噻吩桥连吡啶盐类化合物的合成与电化学性质

设计并合成了3个二取代和三取代的二茂铁-噻吩、二茂铁-联噻吩吡啶盐类化合物： 碘化(E,E)-N-甲基-2,4,6-三{2-[5-(2-二茂铁乙烯基)噻吩-2-基]乙烯基}吡啶盐、 碘化(E,E)-N-甲基-2,6-二{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐、碘化(E,E)-N-甲基-2,4,6-三{2-[5’-(2-二茂铁乙烯基)-2,2’-联噻吩-5-基]乙烯基}吡啶盐。初步研究了这些化合物的电化学性质,结果表明,该类多取代二茂铁吡啶盐具有很好的氧化-还原可逆性,是潜在的电化学分子材料。     

(2,2-双二茂铁基丙烷)-6-甲酸酯的合成与表征

以2,2-双二茂铁基丙烷作为母体制得对应的甲酸,并以此合成了一系列未见文献报道的（2,2-双二茂铁基丙烷）-6．甲酸酯,其结构经1^H NMR,IR及元素分析表征。     

含二茂铁核的硅有机衍生物的合成

合成了一系列含二茂铁核的硅有机衍生物.试图从环戊二烯基三甲基硅烷与FeCl₂在二乙胺存在下制取1,1'-双(三甲基硅烷基)二茂铁,由于Si-C键的断裂,未获预期产物而得二茂铁. 为了合成双有机硅基二茂铁,采用了两种方法.方法之一是从1,1'-二茂铁二钠与相应的三烷基氯硅烷反应制得1,1'-双(三甲基硅烷基)二茂铁、1,1'-双(三丁基硅烷基)二茂铁和1,1'-双(二甲基苯基硅烷基)二茂铁.为了取得单取代硅烷基二茂铁,采用二茂铁锂,但一般得单和双取代衍生物的混合物,它们很难分离;如减少有机氯硅烷用量,则可得纯的单取代乙烯基二乙基硅烷基二茂铁.另一方法是将三甲基-γ-氯丙基硅烷的格氏试剂与二乙酰基二茂铁反应制得含二茂铁核的双叔醇.     

双二茂铁基吡咯衍生物电荷交互通道

以二茂铁炔烃为原料通过“一锅法”环加成反应合成了一系列2,5-双二茂铁基-1-苯基-吡咯衍生物, 包括: 2,5-双二茂铁基-1-(3-三氟甲基苯基)-吡咯(1), 2,5-双二茂铁基-1-(4-氟苯基)-吡咯(2), 2,5-双二茂铁基-1-苯基-吡咯(3), 2,5-双二茂铁基-1-(4-乙基苯基)-吡咯(4)和2,5-双二茂铁基-1-(4-乙氧基苯基)-吡咯(5), 使用元素分析, 傅里叶变换红外(FTIR)光谱, 质谱(MS)和核磁共振(NMR)等手段对化合物进行了结构表征. 采用循环伏安法(CV), 密度泛函理论(DFT)模拟计算研究了苯基上取代基对双二茂铁间电荷交互的影响. 研究发现第一氧化电位(E_a1), 峰电位差(ΔE)与取代基的哈米特常数(σ), 吡咯¹H NMR的化学位移(δ), 吡咯N原子自然轨道(NBO)电荷之间存在显著线性关联; 同时发现, N原子电荷密度升高, 双二茂铁间电荷交互能力减弱, N原子电荷密度降低, 双二茂铁间电荷交互能力提高. 因此这类双二茂铁基吡咯衍生物中N原子电荷密度对双二茂铁间电荷交互起着关键的影响作用.     

双二茂铁基醛亚胺钼（ＶＩ）配合物的合成及催化性能

通过二茂铁甲醛与丙二胺反应得到双二茂铁基醛亚胺配体N~1,N~3-双二茂铁亚甲基丙烷-1, 3-二胺(FcMP), FcMP与MoO_2Cl_2(THF)_2的四氢呋喃溶液作用, 合成了双二茂铁基醛亚胺钼(VI)配合物. 以配合物为催化剂, 叔丁基过氧化氢为氧化剂, 分别以苯乙烯和环己烯为底物, 考察了温度、时间、催化剂量及溶剂对于烯烃均相环氧化反应的催化性能的影响. 结果表明, 在最优实验条件下, 反应12 h, 环己烯的转化率为88%, 环氧环己烷的选择性为98%;苯乙烯的转化率为84%, 氧化苯乙烯的选择性为76%. 催化剂经简单分离可回收使用, 且催化活性基本保持不变. 同时对环氧化反应的机理进行了初步探讨.     

Kinetic and mechanistic studies on the oxidation of hydroxylamine, semicarbazide, and thiosemicarbazide by iron(III) in the presence of triazines

In the presence of 3-(2-pyridyl)-5,6-bis(4-phenyl-sulphonicacid)-1,2,4-triazine disodium salt (PDTS), 3-(4-(4-phenylsulphonic-acid)-2-pyridyl)-5,6-bis(4-phenylsulphonic-acid)-1,2,4-triazine trisodium salt (PPDTS), or 2,4-bis(5,6-bis(4-phenylsulphonic-acid)-1,2,4-triazin-3-yl)pyridine tetra sodium salt (BDTPS), iron(III) oxidizes hydroxylamine to nitrogen gas, semicarbazide to CO₂ and NH₃ and thiosemicarbazide to a disulfide. The corresponding iron product is the 1:3 complex of iron(II) and PDTS, PPDTS, or BDTPS. The kinetics of these reactions was studied by monitoring the iron(II) product by conventional spectrophotometry. The reaction is first order in iron(III). Kinetic evidence was obtained for the formation of 1:1:2 ternary complexes of iron(III), substrate, and sulfonated triazine. Evidence for the ternary intermediate complexes was obtained by ion-exchange studies using ⁵⁹Fe-labeled iron(III) solutions. The dissociation of the ternary complex is identified as the rate-determining step.     

A comparison of some pyridyl-substituted pyrazines as analytical reagents

A comparative study of six 2-pyridyl and 2-(6-methyl-pyridyl) derivatives of pyrazine as chromogenic reagents of the ferroin and cuproin types has established 2,3,5,6-tetrakis(2'-pyridyl)pyrazine as a highly sensitive reagent for iron(II); 2,3-bis(2'-pyridyl)-5,6-dihydropyrazine and 2,3-bis[2'-(6'-methyl pyridyl)]-5,6-dihydropyazine both show high sensitivity and characteristic high selectivity in their reactions with iron(II) and copper(I) respectively-the reaction with copper(I) being almost as sensitive as that given by bathocuproine. The ease with which the highly coloured metal chelates can be extracted into immiscible solvents to give stable solutions makes these reagents useful for the determination of traces of iron and copper.     

Magnetic Properties and Mössbauer Spectra of Binuclear Copper(II) and Tetranuclear Diiron(III)-porphyrin-dicopper(II) Complexes with Schiff-Base Ligands of 2-lmidazolealdehyde and Acetylpyrazine

The binuclear copper(II) and tetranuclear diiron(III)-porphyrin-dicopper(II) complexes with the Schiff-base ligands of N,N′-bis(2-imidazolaldehyde)ethylenediimine, N,N′-bis(2-imidazolaldehyde)-p-phenyldiimine, N,N-bis(acetylpyrazine)-ethylenediimine and N,N′-bis(acetylpyrazine)-p-phenyldiimine have been prepared and characterized. The magnetic data indicated that the spin ground states and the magneic interaction between Cu(II)-Cu(II) or Fe(III)-Cu(II) are dependent on the nature of the bridging ligands. A weak antiferromagnetic interaction between Fe(III) and Cu(II) is evident from the temperature-dependent magnetic measurements. The Mössbauer spectra of iron(III) -porphyrin sites showed an asymmetric quadrupole doublet consistent with high-spin iron(III) S = 5/2.     

Incorporation of hexafluorobutyne into furans or phenols via reaction with iron(0) carbene or vinylketene complexes

Reaction of iron(0) carbene complexes with hexafluorobut-2-yne produces 3,4-bis(trifluoromethylated)furans in a process that is favored for electron-rich carbenes. No traces of furannulation or benzannulation are observed with Group 6 Fischer carbenes. Reaction of hexafluorobut-2-yne with a vinylketene iron(0) complex gives a 2,3-bis-trifluoromethylated phenol.     

Complex Formation of 1,5-Bis(amidomethylsulfonyl)pentane with Copper(II) and Iron(III)

The state of the new antitubercular agent 1,5-bis(amidomethylsulfonyl)pentane in aqueous micellar solution of the nonionic surfactant Bridge 35 and its complexing properties toward copper(II) and iron(III) ions have been studied by spectrophotometry, pH potentiometry (25°C, variable ionic strength), and mathematical modeling. In the concentration range from 5.00 × 10^–5 to 1.00 × 10^–3 M in the presence of Bridge 35, the title compound exists in a neutral monomeric form. It forms 1: 2 mononuclear and 2: 2 binuclear complexes with copper(II) and 1: 1 and 1: 2 mononuclear and 2: 1 binuclear complexes with iron(III). The most favorable structures of 1,5-bis(amidomethylsulfonyl)pentane and its complexes have been simulated in terms of the density functional theory.     

Synthesis and characterization of an iron(II) eta(2)-hydrazine complex

The iron phosphine complex cis-[Fe(DMeOPrPE)2(eta2-N2H4)][BPh4]2 {DMeOPrPE = 1,2-bis[bis(methoxypropyl)phosphino]ethane} was synthesized and structurally characterized. The structure exhibits the first eta2 coordination of hydrazine to iron, which may be relevant to intermediates trapped during nitrogenase turnover. The reaction of I with acid results in the formation of ammonia via a disproportionation reaction.     

Spectrophotometric determination of iron and cobalt with Ferrozine and dithizone

Procedures are described whereby iron (1–50 μg) and cobalt (1–25 μg) are determined spectrophotometrically, iron as iron(II) with the disodium salt of 3-(2-pyridyl)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine (Ferrozine) and cobalt as the cobalt(III) dithizonate complex. The reduction to iron(II) prevents interference of iron(III) in the cobalt determination, and both metals can be determined in the same portion of sample solution. Removal of interference by other metal ions is described.     

Derivatives of 1,1′-bis(diphenylphosphino)ferrocene (dppf): Electrochemistry, complexation and the X-ray structures of 1,1′-bis(diphenylphosphino)osmocene (dppo) and [PdCl2(dppo)]

The oxidative electrochemistry of 1,1′-bis(diphenylphosphino)osmocene (dppo) and 1,1′-bis(diphenylarsino)ferrocene (dpaf) was studied in dichloromethane with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The [MCl₂(P^∩P)] (M = Pd or Pt; P^∩P = dppo or 1,1′-bis(diphenylphosphinoindenyl)iron) complexes were prepared, studied electrochemically and the X-ray structures of dppo and [PdCl₂(dppo)] were determined.     

A C2-symmetric analogue of dppf: synthesis and structures of the indenyl-diphosphine complex 1,3-(Ph2PSe)2(C9H6) and the racemic and meso isomers of the heterobimetallic complex Mo(CO)4(1-PPh2-η-C9H6)2Fe

The preparation, isolation and characterisation of 1,3-bis(diphenylphosphino)indene (1) from indene and chlorodiphenylphosphine is described. The reaction of 1 with selenium gives the diselenide adduct 1,3-bis(diphenylselenophosphino)indene (2) which was characterised crystallographically. Deprotonation of 1 and treatment with ferrous chloride gives the unstable tetraphosphine complex bis(1,3-bis(diphenylphosphino)indenyl)iron(II) (3). Complex 3 decomposes to the diphosphine complex bis(1-diphenylphosphinoindenyl)iron(II) (4) via replacement of one diphenylphosphine substituent per indenyl ligand by a hydrogen atom. Complex 4 was also prepared by treatment of two equivalents of 1-diphenylphosphinoindenide with ferrous chloride. The heterobimetallic complex tetracarbonyl(bis(1-diphenylphosphinoindenyl)iron(II))molybdenum(0) (5) was also prepared and crystal structures of both the meso (5a) and C₂-symmetric racemic (5b) isomers are reported.     

Iron(II) complexes with bio-inspired N,N,O ligands as oxidation catalysts: olefin epoxidation and cis-dihydroxylation

The Rieske dioxygenases are a group of non-heme iron enzymes, which catalyze the stereospecific cis-dihydroxylation of its substrates. Herein, we report the iron(II) coordination chemistry of the ligands 3,3-bis(1-methylimidazol-2-yl)propionate (L1) and its neutral propyl ester analogue propyl 3,3-bis(1-methylimidazol-2-yl)propionate (PrL1). The molecular structures of two iron(II) complexes with PrL1 were determined and two different coordination modes of the ligand were observed. In [Fe(II)(PrL1)(2)](BPh(4))(2) (3) the ligand is facially coordinated to the metal with an N,N,O donor set, whereas in [Fe(II)(PrL1)(2)(MeOH)(2)](OTf)(2) (4) a bidentate N,N binding mode is found. In 4, the solvent molecules are in a cis arrangement with respect to each other. Complex 4 is a close structural mimic of the crystallographically characterized non-heme iron(II) enzyme apocarotenoid-15-15'-oxygenase (APO). The mechanistic features of APO are thought to be similar to those of the Rieske oxygenases, the original inspiration for this work. The non-heme iron complexes [Fe(II)(PrL1)(2)](OTf)(2) (2) and [Fe(II)(PrL1)(2)](BPh(4))(2) (3) were tested in olefin oxidation reactions with H(2)O(2) as the terminal oxidant. Whereas 2 was an active catalyst and both epoxide and cis-dihydroxylation products were observed, 3 showed negligible activity under the same conditions, illustrating the importance of the anion in the reaction.