Search results for "Ferrocene"

Synthèse et caractérisation de phosphine, borane, amine sur plateforme ferrocène polyfonctionnelle

2016

Ferrocene platforms are useful in coordination chemistry and catalysis thanks to their robustness and versatile functionalization. Ferrocene backbone allows the implantation of several key functional groups in a restricted space, inducing close proximity and potential polyfunctional cooperation (see for instance ferrocenyl polyphosphine chemistry). Ansa ferrocene and ferrocene bearing conformational control inducing groups maximizing the proximity of key groups have been widely reported.The first part of this thesis focuses on the synthesis of new borylated cyclopentadienyl, and their use in formation of borylated metallocenes bearing conformational constraints. NMR analysis and DFT calcula…

Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing

2016

Pseudopeptidic receptors containing ferrocene fragments have been prepared and their response to a series of anions was measured by a voltammetry of microparticles methodology. Such water-insoluble compounds yield anion-assisted reversible solid-state oxidations differing in their open-circuit potential and their midpeak potential recorded in cyclic voltammetric measurements. The difference between those potentials provides the individual thermodynamic contributions of electron and proton transfer, revealing that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry. The studied receptors are potentially interesting for potentiometric sensing, showing relat…

New efficient artemisinin derived agents against human leukemia cells, human cytomegalovirus and Plasmodium falciparum: 2nd generation 1,2,4-trioxane…

2015

Abstract In our ongoing search for highly active hybrid molecules exceeding their parent compounds in anticancer, antimalaria as well as antiviral activity and being an alternative to the standard drugs, we present the synthesis and biological investigations of 2nd generation 1,2,4-trioxane-ferrocene hybrids. In vitro tests against the CCRF-CEM leukemia cell line revealed di-1,2,4-trioxane-ferrocene hybrid 7 as the most active compound (IC50 of 0.01 μM). Regarding the activity against the multidrug resistant subline CEM/ADR5000, 1,2,4-trioxane-ferrocene hybrid 5 showed a remarkable activity (IC50 of 0.53 μM). Contrary to the antimalaria activity of hybrids 4–8 against Plasmodium falciparum …

New Internal-Charge-Transfer Second-Order Nonlinear Optical Chromophores Based on the Donor Ferrocenylpyrazole Moiety

2016

A series of new N-arylated ferrocenepyrazole structures, carrying different donor or acceptor substituents in the para position of the aryl ring, has been synthesized by the Chan-Lam cross-coupling reaction. The nonplanar geometric molecular structure of some of these chromophores together with their crystal packing was determined by X-ray diffraction, and the HOMO and LUMO energy levels were evaluated by electrochemical and optical measurements and by density functional theoretical (DFT) calculations. By the investigation of solvent effects and time-dependent DFT (TD-DFT) calculations, the intense electronic absorption band around 270-310 nm was confirmed to be an internal-chargetransfer (…

Solid-State Pyrolyses of Metal Phthalocyanines: A Simple Approach towards Nitrogen-Doped CNTs and Metal/Carbon Nanocables

2006

Solid-state pyrolysis of organometallic precursors has emerged as an alternative method for preparing carbon nanostructures such as carbon nanotubes (CNT) and carbon anions. The morphology of the tubes can be controlled by the nature of the precursors and the pyrolysis procedures, and micrometer long nanotubes, composed of metal carbide wires encased in a graphitic sheath. Cobalt phthalocyanine (CoPc) as well as iron phthalocyanine were pyrolyzed at different temperatures to obtain CNTs. HRTEM and energy-dispersion X-Ray analysis disclosed that the core consisted of long, iron-containing single crystals and that the core was fully surrounded by crystallized graphic carbon. Iron-filled carbo…

Bioconjugates of 1’-Aminoferrocene-1-carboxylic Acid with (S)-3-Amino-2-methylpropanoic Acid and L-Alanine

2010

Formal CH 2 insertion in bioconjugates composed of 1'-aminoferrocene-1-carboxylic acid (Fca) and alanine Boc-Ala-Fca-Ala-OCH 3 gives Fca bioconjugates with the β-amino acid (S)-3-amino-2-methylpropanoic acid (Aib). The novel homologous conjugates of ferrocene were fully characterized by spectroscopic and analytical methods. NMR, CD and IR spectroscopy in concert with DFT calculations suggest that the formal "L-Ala-to-(S)-β-Aib mutations" can exert ferrocene helix inversion due to the different stereogenic carbon atoms of L -Ala and (S)-β-Aib. Furthermore, the mutation (de-)stabilizes the conserved secondary structure with two intramolecular hydrogen bonds, depending on the "mutation site". …

Unexpected C–C bond formation with a ferrocenyl Fischer carbene complex

2020

The Crystal Structure of the THF Adduct of Monolithioferrocene

2015

Single crystals of [Fe(η5-C5H4)(η5-C5H5)]2Li2(thf)4 (1) were obtained from a tetrahydrofuran solution containing monolithioferrocene. The title compound crystallizes in the monoclinic space group P21 with a = 9.6589(5) A, b = 17.4285(9) A, c = 30.3116(15) A, β = 91.911(2)° and V = 5099.8(5) A3 with three independent molecules of 1. All individual molecules feature a non- symmetric almost planar Li2C2 four-membered ring with two shorter (2.118–2.215 A) and two longer Li–C distances (2.257–2.309 A). The lithium cations are each coordinated by two carbanionic atoms of two ferrocenyl substituents and two tetrahydrofuran molecules in a distorted tetrahedral fashion. All ferrocenyl moieties displ…

Preparation, Properties, and Reactivity of (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)chromium(0) as Bulky Isolobal Trimetallo-amide

2015

Nucleophilic substitution of the ethoxy substituent in the Fischer carbene complex (ethoxy)(ferrocenyl)carbene(pentacarbonyl)chromium(0) (1) by ferrocenyl amide [Fc-NH]– [2-H]– gives the hetero trimetallic complex (aminoferrocenyl)(ferrocenyl)carbene (pentacarbonyl)chromium(0) (3). As the Cr(CO)5 fragment is isolobal to oxygen or sulfur 3 can be viewed as an isolobal metallo analogue to diferrocenylamide (Fc)(FcNH)C=O (4) and diferrocenylthioamide (Fc)(FcNH)C=S (5). The impact of the formal replacement of O/S by Cr(CO)5 in 3 is studied with respect to steric and electronic consequences as well as reactivity by spectroscopic, diffraction, electrochemical and theoretical methods.

Tuning Reductive and Oxidative Photoinduced Electron Transfer in Amide‐Linked Anthraquinone–Porphyrin–Ferrocene Architectures

2014

Porphyrin amino acids 3a–3h with meso substituents Ar of tunable electron-donating power (Ar = 4-C6H4OnBu, 4-C6H4OMe, 4-C6H4Me, Mes, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) have been linked at the N terminus to anthraquinone Q as electron acceptor through amide bonds to give Q-PAr dyads 4a–4h. These were conjugated to ferrocene Fc at the C terminus as electron donor to give the acceptor-chromophore-donor Q-PAr-Fc triads 6a–6h. To further modify the energies of the electronically excited and charge-separated states, the triads 6a–6h were metallated with zinc(II) to give the corresponding Q-(Zn)PAr-Fc triads Zn-6a–Zn-6h. The Q-PAr1 dyad (Ar1 = C6H5) was further extended with a second porphyrin PAr2 (…