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Ferrocene Units (ferrocene + unit)

Distribution by Scientific Domains

Chemistry	80%

Selected Abstracts

Ferrocene compounds: methyl 1,-aminoferrocene-1-carboxylate

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2010
Christoph Förster
The title compund, [Fe(C5H6N)(C7H7O2)], features one strong intermolecular hydrogen bond of the type N,H...O=C [N...O = 3.028,(2),Å] between the amine group and the carbonyl group of a neighbouring molecule, and vice versa, to form a centrosymmetric dimer. Furthermore, the carbonyl group acts as a double H-atom acceptor in the formation of a second, weaker, hydrogen bond of the type C,H...O=C [C...O = 3.283,(2),Å] with the methyl group of the ester group of a second neighbouring molecule at (x, ,y , , z , ). The methyl group also acts as a weak hydrogen-bond donor, symmetry-related to the latter described C,H...O=C interaction, to a third molecule at (x, ,y , , z + ) to form a two-dimensional network. The cyclopentadienyl rings of the ferrocene unit are parallel to each other within 0.33,(3)° and show an almost eclipsed 1,1,-conformation, with a relative twist angle of 9.32,(12)°. The ester group is twisted slightly [11.33,(8)°] relative to the cylopentadienyl plane due to the above-mentioned intermolecular hydrogen bonds of the carbonyl group. The N atom shows pyramidal coordination geometry, with the sum of the X,N,Y angles being 340,(3)°. [source]

"Tail,Tail Dimerization" of Ferrocene Amino Acid Derivatives

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2010
Daniel Siebler
Abstract Acid anhydrides of N-protected 1,-aminoferrocene-1-carboxylic acid (Fca) have been prepared and spectroscopically characterized (protection group Boc, Fmoc, Ac; 4a,4c). The structure of the Boc-derivative 4a has been determined by single-crystal X-ray crystallography. An intramolecular N,H···O hydrogen bond involving the carbamate units results in a ring structure containing the two ferrocene units, the anhydride moiety, and the hydrogen bond. In the crystal, the individual molecules are connected by intermolecular N,H···O hydrogen bonds of the carbamate unit. Experimental and theoretical studies suggest that the ring motif is also a dominant species in solution. Electronic communication across the anhydride moiety is found to be very weak as judged from electrochemical, spectroscopic, and theoretical experiments. [source]

Synthesis and Characterization of Radical Cations Derived from Mono- and Biferrocenyl-Substituted 2-Aza-1,3-butadienes: A Study of the Influence of an Asymmetric and Oxidizable Bridge on Intramolecular Electron Transfer

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005
Vega Lloveras
Abstract The synthesis and study of structural and electronic properties of mono-ferrocenyl ,-conjugated complexes 5a,d, whose electronic characteristics have been systematically varied by introducing an electron-donating or electron-withdrawing substituent either at the 1-position or at the 4-position of the 2-aza-1,3-butadiene moiety linked to the ferrocenyl unit, are presented. The structural and electronic properties of the homobimetallic complex 5f, with two ferrocene units linked through the asymmetric and oxidizable 2-aza-1,3-butadiene bridge, is also reported. The crystal structures of complexes 5b, 5d, and 5f show a large degree of conjugation in this family of compounds. Complexes 5 show a rich electrochemical behavior due both to the oxidation of ferrocenyl units and the 2-aza-1,3-butadiene bridge, as revealed by cyclic voltammetry. Radical cations 5+· were prepared from 5 by coulometric oxidations following their generation by absorption spectroscopy. The electronic properties of all reported neutral and oxidized ,-conjugated complexes have been investigated by means of UV/Vis,near-IR, EPR and 57Fe Mössbauer spectroscopy. The detailed study of mono-oxidized species 5a+·,5f+· has permitted the determination of the influence of an asymmetric bridge with an electroactive character on the intramolecular electron transfer (IET) phenomenon, thus demonstrating that the 2-aza-1,3-butadiene bridge promotes the IET between the two metallic units of 5f+· through two different pathways. The experimental data and conclusions are supported by DFT computations (B3LYP/3-21G*) and time-dependent DFT methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Modulation of the Communication between Redox Centers in a Tris(ferrocene)-tren Ligand by Complexation of Lanthanide Ions

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2003
Marie Heitzmann
The tripodal ligand L built on the tren platform and bearing three chemically equivalent ferrocene units was prepared and characterized. Electrochemical investigations indicate that electrostatic communication occurs between the three ferrocene groups in L, which leads to the observation of two distinct voltammetric waves. The electrochemical communication between the three ferrocene moieties is disrupted in 1:1 (L:M3+) type complexes formed between L and Y3+ or Eu3+ metal cations and their electrochemical response tends towards that of a single three-independent-electrons oxidation wave. Modulation of the electrochemical properties of L in the presence of lanthanide ions might be exploited with a view to their electrochemical sensing in organic and aqueous media. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Ferrocenyl-functionalized long chain branched polydienes

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2009
Frederik Wurm
Abstract A convenient two-step approach for the synthesis of ferrocenyl-functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end-capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent ABn + AR type of copolymerization with mono- and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2 - and fc2SiMe-units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2518,2529, 2009 [source]