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The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocene-based Lewis bases have found utility as metalloligands in a wide variety of applications. The coordination chemistry of cyanoferrocenes however, is underexplored. Herein, we describe a new synthetic protocol for the generation of cyanoferrocenes. The coordination chemistry of these metalloligands to [Cu(NCMe)4][PF6], [(PPh3)2Cu(NCMe)2][PF6] and [(dppf)Cu(NCMe)2][PF6] salts has been explored, providing crystallographic evidence of cluster and polymeric forms of 1,1?- and 1,2-dicyanoferrocene complexes. The stability of the complexes and ligand dissociation were found to be strongly solvent-dependent.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Quality Control of Ferrocenemethanol. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

Electron transfer (ET) reactions in ionic liquid (IL)|organic solvent (1,2-dichloroethane, DCE) and IL|water mixtures were investigated using a Pt disk ultramicroelectrode (UME) along with ferrocene (Fc) and ferrocenemethanol (FcCH2OH) redox probes as electroactive species dissolved in the respective mixtures. The IL utilized was tributylmethylphosphonium methyl sulfate (P4441CH3SO4). The diffusion coefficient of each redox species was determined at each incremental increase of DCE or water to the IL using a chronoamperometric technique that is concentration independent. The IL|DCE mixture exhibited little change in the Fc diffusion coefficient, DFc, up to a DCE mole fraction (chiDCE) of 0.5; the observed value, 2.0 × 10-8 cm2 s-1, agrees well with that typically reported for ILs in the literature. After which, the DFc quickly rose to a value commonly found in conventional molecular solvents, 1.3 × 10-5 cm2 s-1 (at chiDCE = 0.8). An analogous result was not observed for IL|water mixtures using FcCH2OH, such that DFcCH2OH varied from 0.2 to 1.2 × 10-9 cm2·s-1 at a chiH2O of 0 to 0.8. It was proposed that a large increase in the DFc in the IL|DCE mixture versus DFcCH2OH in the IL|water series was owing to P4441CH3SO4’s more hydrophobic character. Its hydrophobicity was quantified by measuring the formal ion transfer potentials of the IL component ions at a water|DCE immiscible interface.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The highest nonlinear optical bulk efficiency for a 2-(4-nitro-phenyl)ethenylferrocene (140 times that of urea) has been achieved for E-4 owing to a favourable noncentrosymmetrical packing in which all molecules are perfectly aligned (P1 space group).

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ethynylferrocenyl derivatives of 2,7-acridine (1, 2), 9-N-acridone (4), and 2-anthraquinone (6) are described. (Z)-10-(2-iodo-1-ethenylferrocene)-9(10H)-acridinone (3), an intermediate in the formation of 4, N-Fc(CH2)n-acridone (5; n = 8, 11), 1-Fc-anthraquinone (7), and (E)-(2-FcC=C)-anthraquinone (8) were also investigated. The X-ray structures of 3 and 6 were determined. B3LYP calculations, UV/vis spectroelectrochemistry, cyclic voltammetry, and ESR spectra were used to probe the ground and excited states of both the neutral and oxidized compounds. Emission is observed from oxidized, but not neutral, 4 and 6; however, 1, 2, and 8 are fluorescent. Surprisingly, emission is reduced upon oxidation of 2 and 8, which appears to correlate with the greater distortion in the excited compared to ground states.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Convergent synthesis of a redox-stable nonaferrocenyl dendrimer using a tritopic dendron with disrupted conjugation is described.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The mechanism of electron transfer of ferrocenylmethanol through the self-assembled monolayer (SAM) of mercaptosuccinic acid (MSA) on gold was investigated. A key finding is that the hydrogen-bonded FcMeOH plays the role of a mediator in the electron transfer involving the physically adsorbed glucose oxidase at the MSA SAM surface. The space-conformation of the hydrogen-bonding between FcMeOH and MSA was obtained by computational methods. The FcMeOH interacts with MSA via the strong hydrogen bond with the short distance around 1.9 A at two different binding sites, approving the statements of hydrogen-bonding. The intermolecular hydrogen-bonding between redox mediator (FcMeOH) and the artificial self-assembled monolayer (MSA) is evident, and the mechanistic study of heterogeneous electron transfer kinetics is meaningful for the biosensor applications.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Triazole-based novel dendrimers with ferrocenyl surface groups have been achieved through click chemistry, both by divergent and convergent approaches. The presence of more ferrocenyl and triazolyl units in dendrimers 1-4 alters the current potential curve in the voltammogram and also the absorption coefficient in the UV-vis spectrum.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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This paper describes a simple and miniaturized microdroplet chip (muchip) that is constructed with a silica nanochannel (SNC)-assisted electrode array and a hydrophobic paper cover (SNC&P-muchip). Vertically aligned SNCs with uniform pore size of 2?3 nm in diameter and negatively charged surface can significantly accelerate the mass transport of the positively charged tris(2,2′-bipyridyl) ruthenium (II), resulting in a remarkably enhanced electrochemiluminescence (ECL) signal. The SNC-assisted electrode array was coupled to a low cost paper cover to achieve simultaneous detection of six samples in 1 min. The feasibility and universality of the SNC&P-muchip was evaluated by detecting a series of alkaloidal drugs both in buffers and in human serum. The performance of the SNC&P-muchip was fully validated with respect to linearity (0.9999 > R > 0.9939), sensitivity (limits of detection from 1.799 nM to 11.43 nM), and accuracy (recovery rate between 94.38% and 109.12%). The facile and economic SNC&P-muchip shows promising potential for rapid drug detection in complex biofluids.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion