Search results for "Ferrocene"
showing 10 items of 306 documents
Highly Functionalized Brønsted Acidic/Lewis Basic Hybrid Ferrocene Ligands: Synthesis and Coordination Chemistry
2019
International audience; A general challenging issue in the synthesis of hemilabile ferrocene ligands is the access to highly functionalized ferrocene starting materials. These can bear donor/acceptor atoms, additional functional and structuring spectator substituents, but the preparation of such species poses general synthetic difficulties. We report herein alternative synthetic routes to hybrid ferrocene donors such as tert-butylated phosphanylcarboxylic acids and their corresponding aldehydes. These hybrid ambiphilic species that combine Brønsted-acidic and Lewis-basic functional moieties in their structure were characterized by multinuclear NMR and single-crystal X-ray diffraction analys…
C2-Symmetric Ferrocene-Bis(ureido)peptides : Synthesis, Conformation and Solid-State Structure
2009
The extension of peptide derivatives of ferrocene-1,1'-dicarboxylic acid by formal insertion of NH units between ferrocene and peptide strands results in ferrocene-bis(ureido)-peptides. Experimentally, alanine and dialanine methyl esters were attached to the 1- and 1'-position of 1,1'-diiso-cyanoferrocene to give the corresponding bis(ureido)peptide derivatives 3 and 4. The conformation of 3 has been determined in the solid state by X-ray crystallography. In solution the preferred conformation of 3 and 4 has been elucidated by NMR, IR and CD spectroscopy in concert with DFT calculations. The secondary structure of ferrocene―bis(ureido)peptides 3 and 4 is determined by double bifurcated intr…
Transfer of Some Alkyl Substituted Ferrocenes from Water to Cationic Surfactant Micelles Studied by Kinetic Method
1994
Abstract Binding of ferrocene and its 1,1′-dimethyl and n -butyl derivatives to dodecyl and tetradecyltrimethylammonium nitrate micellar aggregates has been studied at 20.0°C and ionic strength 0.02 tool dm -3 by examining the micellar retarding effects on the rates of iron(III) oxidation of these substrates. Solubilization of the ferrocenes in the cationic micellar phase increases as the substrate hydrophobic character increases and, to a lesser extent, as the surfactant hydrocarbon chain length becomes longer. The critical micelle concentrations of the surfactants used and the incremental free energy of transfer of methylene groups of both the substrate and the surfactant from the aqueous…
Towards the Next Generation of Lochmann-Schlosser Superbases: A Potassium Neopentyl/Alkoxy Aggregate used in the Tetra-Functionalization of Ferrocene
2018
Lochmann-Schlosser superbases are formed by mixing alkyllithium with potassium alkoxides. These reagents could prove their synthetic usefulness and reliability in many reactions over five decades. However, despite many efforts, the real source of the exceptional reactivity remained a secret. The seemingly manageable system of four components (lithium, potassium atoms, alkyl groups, and alkoxy groups) and their interaction is obscured by poor solubility and fierce reactivity. Recent progress was achieved by using neopentyllithium, leading to alkane-soluble aggregates with varying lithium/potassium content and a flexible alkyl/alkoxy ratio. Herein, we isolated two new alkane-soluble alkyl/alk…
Fine tuning of the catalytic effect of a metal-free porphyrin on the homogeneous oxygen reduction.
2011
The catalytic effect of tetraphenylporphyrin on the oxygen reduction with ferrocene in 1,2-dichloroethane can be finely tuned by varying the molar ratio of the acid to the catalyst present in the solution. The mechanism involves binding of molecular oxygen to the protonated free porphyrin base, in competition with ion pairing between the protonated base and the acid anion present.
Near infrared dyes by combination of squaraine and ferrocene chromophores
2000
Abstract Squaraines represent a class of compounds which attracts a lot of attention in materials science. A synthetic sequence for the preparation of the symmetrical squaraines 12a , b , which contain ferrocene units as electron donors, is described. The compounds exhibit, in dichloromethane or chloroform, two intense absorption bands. One of them is located at 641/650 nm—a normal region for squaraines; however, the other band is strongly shifted to long wavelengths and has its maximum at 921/961 nm. Alkyl sidechains enhance the solubility of 12a , b , which represent a new type of NIR dyes.
New ferrocene-containing copolyesters
1995
We have synthesized four new ferrocene monomers (three diols and one diester). The redox potential of these ferrocene derivatives varies between 0 mV and 230 mV due to different degrees of ring alkylation. Amorphous and liquid crystalline copolyesters were prepared with these monomers in the polymer main chain. Cyclovoltammetric measurements show that the redox potential of the ferrocene units is increased by about 40 mV upon polymer formation (esterification). Since the ester group is 4 to 6 σ-bonds away from the ferrocene unit this increase is probably caused by some charge-transfer interaction through space. First rheological measurements show an unusual rubber-like behaviour of the ferr…
The use of metallocenic esters of n-hydroxysuccinimide for metallohapten synthesis
1991
Different organometallic markers have been described in a new technique for the labelling of many drugs. Thus metallocenic esters of [M = (;CO)3CrC6H5; (;CO)3CrC6H5(;CH2)3; η-C5H5FeC5H4; (;CO)3MnηC5H4; (;CO)3MnηC5H4COCH2CH2; ηC5H4(;ηC5H5)Co+PF−6] react with primary or secondary amine drugs [DRUGNHR] for a psychostimulant drug: amphetamine; tricyclic antidepressants—desipramine and nortriptyline; a vasodilator—histamine; an adrenergic substance—norfenefrine; and for a central stimulant—meth-amphetamine, to give the metallohaptens MCON(;R)—DRUG. All these compounds have been fully characterized by different analytical methods and have potentialities for biological assays. This synthetic route…
“Tail–Tail Dimerization” of Ferrocene Amino Acid Derivatives
2010
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 a…
Ferrocenyl-Labeled Sugar Amino Acids: Conformation and Properties
2012
Novel organometallic sugar amino acid conjugates 1–5 have been prepared by amide coupling of O-protected N-acetylmuramic acid and iso-muramic acid (2-[3-amino-2, 5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxypropanoic acid) with 1-aminoferrocene, 1-aminoferrocene-1′-carboxylic acid (H-Fca-OH), or 1, 1′-diaminoferrocene, respectively. The influence of the ferrocenyl moiety and presence of additional remote potential hydrogen atom acceptors and donors at the ferrocenyl core on the conformation and lipophilicity is investigated by TLC, IR, NMR, and CD spectroscopic methods augmented by density functional calculations. Furthermore, the redox potential of the ferrocene/ferrocenium couple is tuned by…