Mössbauer Spectroscopic Studies of Supported α-Fe2O3 and Fe Catalysts II: The Effect of the Second Metal Addition

The effect of the addition of a second metals such as Zn and Ni on the calcinaton and reduction of alumina, magnesia and silicasupported iron catalysis with total iron loading of 5wt% is investigated by Mössbauer spectroscopy. It is shown that the reducibility of supported α-Fe₂O₃ is gradually increased by adding the second metal. The values of the magnetic hyperfine field obtained from Mössbauer spectra for the Zn or Ni-added α-Fe₂O₃ or Fe catalysts decreased with increasing second metal loading.     

Synthesis, structure, and dynamics of six-membered metallacoronands and metallodendrimers of iron and indium

In the reaction of the N-substituted diethanolamines (H(2)L(1-3)) (1-3) with calcium hydride followed by addition of iron(III) or indium(III) chloride, the iron wheels [Fe(6)Cl(6)(L(1))(6)] (4) and [Fe(6)Cl(6)(L(2))(6)] (6) or indium wheels [In(6)Cl(6)(L(1))(6)] (5), [In(6)Cl(6)(L(2))(6)] (8) and [In(6)Cl(6)(L(3))(6)] (9) were formed in excellent yields. Exchange of the chloride ions of 6 by thiocyanate ions afforded [Fe(6)(SCN)(6)(L(2))(6)] (7). Whereas the structures of 4, 5 and 7 were determined unequivocally by single-crystal X-ray analyses, complexes 8 and 9 were characterised by NMR spectroscopy. Contrary to what is normally presumed, the scaffolds of six-membered metallic wheels are not generally rigid, but rather undergo nondissociative topomerisation processes. This was shown by variable temperature (VT) (1)H NMR spectroscopy for the indium wheel [In(6)Cl(6)(L(1))(6)] (5) and is highlighted for the enantiotopomerisation of one indium centre [ 1/6[S(6)-5]<==>[1/6[S(6)-5']]. The self-assembly of metallic wheels, starting from diethanolamine dendrons, is an efficient strategy for the convergent synthesis of metallodendrimers.     

Molecular magnet based on the FeII,III complex with squaric acid

The reaction of Fe^II and Fe^III salts with tetrabutylammonium squarate in an aqueous solution gives rise to a new molecular magnet (T _c = 8.6 K).     

硼化合物的研究——Ⅴ.氢硼酸π-芳烃-π-环戊二烯基铁的合成和性质

本文研究了氢硼酸根(B_(12)H_(12)~(2-)、B_(10)H_(10)~(1-)、B_(11)H_(14)~-)和π-芳烃-π-环戊二烯基铁阳离子的反应,合成了36个氢硼酸π-芳烃-π-环戊二烯基铁化合物。通过元素分析和红外光谱测定确定了化合物的组成。部份化合物还作了~1H NMR鉴定。对化合物的性质,包括它们的热行为,进行了较详细的研究。DTA仪测得的结果表明,(1)当阳离子相同时,化合物的热稳定性的顺序为:[ArFeC_5H_5]_2B_(12)H_(12)>[ArFeC_5H_5]_2B_(10)H_(10)>[ArFeC_5H_5]B_(11)H_(14);(2)当氢硼酸根相同时,其热稳定性受芳环上取代基的影响。     

一例可分离的双核铁氢自由基阳离子

成功分离得到了一例双核铁氢自由基阳离子盐cis-[Fe₂Cp₂（μ-H）（μ-PPh₂）（CO）₂]^·+[Al（OC（CF₃）₃）₄]^-（cis-1^·+[Al（OC（CF₃）₃）₄]^-）晶体，并使用单晶X射线衍射、电子顺磁共振、红外光谱、紫外-可见光谱以及密度泛函理论对它进行了表征和理论计算。电子顺磁共振和密度泛函理论计算分析表明，自由基的自旋密度主要均等分布于2个铁原子上。     

三核铁甲酸配合物的热解过程及其若干催化活性碎片的研究

三重桥氧三核铁甲酸配合物[Fe_3(μ_3-O)(μ-O_2CH)_6(H_2O)_2·(O_2CH)]·2H_2O的热反应行为十分有趣,其在热解过程某阶段失去部分配体后的碎片能活化乙炔进行加氢或加水反应生成乙烯、乙醛和丙酮,为揭示这些活性碎片的本质,我们应用了原位红外光谱(in situ IR),热重(TG)、差热分析(DTA),气相色谱(GC)、X-射线粉未衍射(XRD)和质谱(MS)等手段综合研究该化合物的热解过程,求出各热解碎片的组成,并研究它们在不同条件下的反应性能.本文报道它们相互验证的定性及定量结果.     

Effect of Thiourea on the Kinetics of the Hydrogen Evolution Reaction at Iron and the Transport of Hydrogen through a Steel Membrane in Solutions of C<Subscript>2</Subscript>H<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O-HCl

The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H₂O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum.     

Synthesis, biochemical properties and molecular modelling studies of organometallic specific estrogen receptor modulators (SERMs), the ferrocifens and hydroxyferrocifens: evidence for an antiproliferative effect of hydroxyferrocifens on both hormone-dependent and hormone-independent breast cancer cell lines

A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions.