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Robert F. Kirchner Gilda H. Loew Ulrich T. Mueller-Westerhoff 《Theoretical chemistry accounts》1976,41(1):1-6
An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations. 相似文献
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Serguei Savilov Lars Kloo Alexei Kuznetsov Boris Popovkin Andreas Fischer 《无机化学与普通化学杂志》2003,629(14):2525-2528
Single crystals of [Fe(Cp)2]3(Bi2Cl9)·thf were obtained from a thf solution containing ferrocene and BiCl3. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P212121 [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit. 相似文献
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J.P. Hurvois 《Journal of organometallic chemistry》2005,690(7):1829-1839
The behaviour of chemically or electrochemically generated ferrocenium cations has been studied in some polar organic solvents (DMF, DMSO, acetonitrile, acetone, methylene chloride) under molecular oxygen. Adducts between oxygen and ferrocenium species can differently evolve according to the solvent (oxidizable or not) and the absence or the presence of another reagent. A rapid decomposition of ferrocenium cations is observed in the absence of another substrate. In the presence of some substrates and antioxidants, the stability of ferrocenium cations towards molecular oxygen notably increases and in some cases redox reactions take place with formation of ferrocene. 相似文献
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《Electroanalysis》2005,17(21):1919-1923
We report a reference electrode for direct use in tetrahydrofuran (THF) at low temperatures. A reference solution containing equimolar amounts of ferrocene/ferrocenium hexafluorophosphate (Fc/Fc+) are prepared to give a 4 mM solution in THF that contains tetrabutylammonium hexafluorophosphate (TBAF) supporting electrolyte thus, minimizing liquid junction potentials. The reference solution is added to a sealed glass tube with a porous frit at one end, and a platinum wire is inserted into the tube. The reference electrode assembly is then inserted into a THF test solution. Potentiometric measurements show that the system responds in the expected Nernstian fashion over the concentration and temperature ranges, 4 mM to 40 μM and 20 °C to ?45 °C respectively. In addition, it is shown by steady–state cyclic voltammetry at a platinum microelectrode that the chemical reactivity of ferrocenium hexafluorophosphate (Fc+) otherwise seen in THF is suppressed by ion‐pairing with PF using tetrabutylammonium hexafluorophosphate (TBAF) as the supporting electrolyte. 相似文献
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The first-order kinetics of the decomposition of ferrocenium ion (Fc+) and its substitution derivatives have been studied in aqueous sulfuric acid and in the presence of excess Ce(IV) ion. The observed first-order rate constant (kobs) is expressed as kobs = kd for the acyl-substituted ferrocenium ions and kobs = kd+ kox[Ce(IV)]o for the unsubstituted and alkyl-substituted ferrocenium ions. Electron-donating alkyl substituents stabilize the ferrocenium ion whereas electron-withdrawing acyl substituents make it less stable. The order of relative stability toward decomposition is 1,1′-dimethyl Fc+ ≥ butyl Fc+ > 1,1-dimethylpropyl Fc+ > Fc+ > > formyl Fc+ > acetyl Fc+ > > benzoyl Fc+. A mechanism to interpret the kinetics is also given. 相似文献
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Ferrocenylmethyldimethylamine, FcCH2NMe2, reacts with CH2Cl2 in either the presence or absence of non-coordinating counterions to give equimolar amounts of the bis(ferrocenylmethyl)dimethyl ammonium salts (FcCH2)2NMe2+X− (X−=PF6−, SbF6−, BPh4− or Cl−, 1a–d) and the corresponding protonated ammonium salts FcCH2NMe2H+ which have been isolated as the SbF6− and Cl− salts 2b,d. The reaction proceeds via fragmentation of an intermediate quaternary chloromethylated ammonium ion to chloromethylferrocene, FcCH2Cl, and dimethyliminium chloride NMe2CH2+Cl−. The parent amine acts as a nucleophile toward FcCH2Cl to give 1a–d and as a base toward NMe2CH2+ to give FcCH2NMe2H+, NMe2H and (Me2N)2CH2. The FcCH2Cl intermediate is intercepted by NEt3 while KCN or LiH do not successfully compete with FcCH2NMe2. A new, non-toxic, selective, high-yield route to 1d is also presented. Electrochemistry and UV–vis spectroelectrochemistry reveal, that the two identical redox centers in 1a–d are essentially non-interacting. Individual E1/2 values have been determined for different solvents by digital simulation. The corresponding ferrocenium salts were prepared by either chemical or electrochemical means and accordingly characterized. Our studies are augmented by X-ray structure analyses of 1b, 1d and 2d. 1d contains three different cation conformers and four molecules of water per unit cell. The latter are hydrogen bonded to the chloride counterions to form one-dimensional infinite chains parallel to the a axis. 相似文献
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Abby R O'Connor Chip Nataro James A Golen Arnold L Rheingold 《Journal of organometallic chemistry》2004,689(14):2411-2414
A new chemical oxidant [N(4-C6H4Br)3][B(C6F5)4], was prepared and used to synthesize [Fe(C5H5)2][B(C6F5)4]. The crystal structure of [Fe(C5H5)2][B(C6F5)4] was determined. 相似文献
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