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Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs

A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs

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

 

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Toward the development of molecular wires: Ruthenium(II) terpyridine complexes containing polyferrocenyl as a spacer

The preparations of multinuclear supramolecules assembled from 1,1?-bis(terpyridyl)ferrocene, 1,1?-bis(terpyridyl)biferrocene, and 1,1?-bis(terpyridyl)triferrocene (tpy-(fc)n-tpy, n = 1-3) redox-active moieties with Ru2+ metal centers are described. The electrochemical measurements of the Ru2+ complexes of tpy-(fc) n-tpy (1a (n = 1); 1b (n = 2); 1c (n = 3)) are dominated by the Ru2+/Ru3+ redox couple (E1/2 from 1.35 to 1.38 V), Fe2+/Fe3+ redox couples (E1/2 from ?0. 4 to ?1.0 V), and tpy/tpy-/tpy2- redox couples (E 1/2 from -1.3 to -1.5 V). The appreciable variations detected in the Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the spacer and the Ru2+ metal centers. Coordination of Ru2+ metal centers to tpy-(fc)n-tpy results in a red-shifted and more intense 1[(d(pi) Fe)6] ? 1[(d(pi)Fe) 5] – (pi*tpyRu)1] transition in the visible region. The observed red-shifted absorption from 526 nm in the monomeric [Ru(fctpy)2]2+ complex to ?560 nm in 1b and 1c reveals that there is a qualitative electronic coupling within the ferrocenyl array. The Fe-Fe interactions result in a red characteristic of the 1[(d(pi)Fe)6] ? 1[(d(pi)Fe)5(pi*tpy Ru)1] MMLCT transition.

Toward the development of molecular wires: Ruthenium(II) terpyridine complexes containing polyferrocenyl as a spacer

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

 

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Recent Advances in the Development of Organic and Organometallic Redox Shuttles for Lithium-Ion Redox Flow Batteries

In recent years, redox flow batteries (RFBs) and derivatives have attracted wide attention from academia to the industrial world because of their ability to accelerate large-grid energy storage. Although vanadium-based RFBs are commercially available, they possess a low energy and power density, which might limit their use on an industrial scale. Therefore, there is scope to improve the performance of RFBs, and this is still an open field for research and development. Herein, a combination between a conventional Li-ion battery and a redox flow battery results in a significant improvement in terms of energy and power density alongside better safety and lower cost. Currently, Li-ion redox flow batteries are becoming a well-established subdomain in the field of flow batteries. Accordingly, the design of novel redox mediators with controllable physical chemical characteristics is crucial for the application of this technology to industrial applications. This Review summarizes the recent works devoted to the development of novel redox mediators in Li-ion redox flow batteries.

Recent Advances in the Development of Organic and Organometallic Redox Shuttles for Lithium-Ion Redox Flow Batteries

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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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Application of 1293-65-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1293-65-8, Name is 1,1′-Dibromoferrocene, molecular formula is C10Br2Fe. In a article£¬once mentioned of 1293-65-8

A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions

A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), is capable of conducting hydrogen atom transfer (HAT) reactions much more efficiently than the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (Ered vs SCE = 1.03 V), compared to that of 2 (Ered vs SCE = -0.1 V). The HAT mechanism of 1 varies between electron transfer followed by proton transfer and one-step concerted proton-coupled electron transfer, depending on the one-electron oxidation potentials of substrates. To the best of our knowledge, this is the first example showing that metal(III)-aqua complex can be an effective H-atom abstraction reagent.

A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions

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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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Reference of 1293-65-8, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.1293-65-8, Name is 1,1′-Dibromoferrocene, molecular formula is C10Br2Fe. In a Article£¬once mentioned of 1293-65-8

Modular Synthesis of Fischer Biscarbene Complexes of Chromium

Aromatic and (hetero)aromatic chromium aminocarbenes were lithiated on the (hetero)aromatic ring and transmetalated with ZnBr2. The subsequent Pd(PPh3)4- or PdCl2(XantPhos)-catalyzed Negishi reaction with dibromoarenes or chromium alkoxy-/aminocarbenes bearing bromine atoms yielded bisaminocarbene or mixed bisalkoxyaminocarbene complexes of chromium. This methodology allows easy access to the biscarbene complexes containing poly(hetero)aromatic bridges, such as biphenylene, bithienylene, tetrathienylene, 1,1?-ferrocenylene, and others. In total, 18 new biscarbene complexes, including two containing both chromium and tungsten, were synthesized in this fashion. The electrochemical behavior of the biscarbenes obtained exhibits electronic communication between the metals.

Modular Synthesis of Fischer Biscarbene Complexes of Chromium

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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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Synthetic Route of 1293-65-8, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1293-65-8, molcular formula is C10Br2Fe, introducing its new discovery.

Kinetically stabilized 1,1′-bis[(E)-dipnosphenyl]ferrocenes: syntheses, structures, properties, and reactivity

Kinetically stabilized 1,1′-bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallo-graphic analyses. The electronic structures of the 1,1′-bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic vol-tammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1′-bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1′-bis[(Z)-diphosphenyl]ferrocene group 6 metal tetracarbonyl complexes, [M(CO) 4{(Z,Z)-(BbtP=PC 5H4)2Fe}] (M = Cr, Mo, and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1H, 13C, and 31PNMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d? pi*p=p electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.

Kinetically stabilized 1,1′-bis[(E)-dipnosphenyl]ferrocenes: syntheses, structures, properties, and reactivity

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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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A functionalized pyridinyl ligand containing binuclear biferrocene

A biferrocenyl ligand containing a pyridinyl moiety which can introduce a degree of flexibility between the metal-binding domains for metallosupramolecules was prepared. The X-ray structural determination and the electrochemical measurement for this new functionalized pyridinyl biferrocene were also reported.

A functionalized pyridinyl ligand containing binuclear biferrocene

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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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BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS

Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group -P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the -P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group -P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the -P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the alpha position to the P-C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS

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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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Redox control of a dendritic ferrocenyl-based homogeneous catalyst

The application of a dendrimer in a redox-switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well-defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1-octen-3-ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron-poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.

Redox control of a dendritic ferrocenyl-based homogeneous catalyst

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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 Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1?-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1?-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1?-difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1?-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

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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