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Photocatalytic oxidation of iron(II) complexes by dioxygen using 9-mesityl-10-methylacridinium ions

Photocatalytic oxidation of iron(ii) complexes by dioxygen occurred using the organic photocatalysts, 9-mesityl-10-methylacridinium ions (Acr+-Mes) and 2-phenyl-4-(1-naphthyl) quinolinium ions (QuPh+-NA), in the presence of triflic acid in acetonitrile under visible light irradiation. The electron-transfer state of Acr+-Mes produced upon photoexcitation oxidized the iron(ii) complexes, whereas it reduced dioxygen with protons to produce iron(iii) complexes and H2O2.

Photocatalytic oxidation of iron(II) complexes by dioxygen using 9-mesityl-10-methylacridinium ions

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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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Indirectly connected bis(N-Heterocyclic Carbene) bimetallic complexes: Dependence of metal-metal electronic coupling on linker geometry

Reaction of l,l’,3,3′-tetra(tert-amyl)benzobis(imidazolylidene) (1) with 2 equiv of FcN3 or FcNCS afforded bisadducts [(FcN3) 2(1)] (2) or [(FcNCS)2(1)] (3), respectively (Fc = ferrocene). To the best of our knowledge, these represent the first examples of complexes comprising metals indirectly connected to the carbene atoms of N-heterocyclic carbenes (NHCs) via their ligand sets. Cyclic and differential pulse voltammetry indicated that bis(NHC) 1 facilitated significant electronic coupling between ferrocene centers in 2 (DeltaE = 140 mV), but not in 3. We believe the different degrees of electronic interaction are due to geometric factors: the triazene linker in 2 is nearly coplanar with the bis(NHC) scaffold, whereas the isothiocyanate linker is orthogonal, as determined by X-ray crystallography. Employing this “indirect connection” strategy should enable tuning of metalmetal interactions by simple alteration the organic linker between NHC and MLn fragments rather than complete redesign thereof. Given that NHC-reactive azide or isothiocyanate groups can be incorporated into both organic and inorganic compounds, this approach is envisioned to facilitate access to otherwise inaccessible catalysts and materials.

Indirectly connected bis(N-Heterocyclic Carbene) bimetallic complexes: Dependence of metal-metal electronic coupling on linker geometry

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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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Reorganization energies of diprotonated and saddle-distorted porphyrins in photoinduced electron-transfer reduction controlled by conformationaldistortion

Kinetics of photoinduced electron transfer from a series of electron donors to the triplet excited states of a series of nonplanar porphyrins, hydrochloride salts of saddle-distorted dodecaphenylporphyrin ([H 4 DPP]Cl 2 ), tetrakis(2,4,6-trimethylphyenyl)porphyrin ([H 4 TMP]Cl 2 ), tetraphenylporphyrin ([H 4 TPP]Cl 2 ), and octaphenylporphyrin ([H 4 OPP]Cl 2), were investigated in comparison with those of a planar porphyrin, zinc [tetrakis(pentafluorophenyl)]porphyrin [Zn(F 20 TPP)(CH 3 CN)], in deaerated acetonitrile by laser flash photolysis. Theresulting data were evaluated in light of the Marcus theory of electron transfer, allowing us to determine reorganization energies of electron transfer to be 1.21 eV for [H 4 TMP]Cl 2 ,1.29 eV for [H 4 TPP]Cl 2 , 1.45 eV for [H 4 OPP]Cl 2 , 1.69 eV for [H 4 DPP]Cl 2 , and 0.84 eV for [Zn(F 20 TPP)(CH 3 CN)]. The reorganization energies exhibited a linear correlation relative to the out-of-plane displacements, which represent the degree of nonplanarity. The rate of electron-transfer reduction of diprotonated porphyrins is significantly slowed down byconformational distortions of the porphyrin ring. This indicates that t he reorganization energy of electron transfer is governed by structural change, giving a larger contribution of inner-sphere bond reorganizationenergy rather than outer-sphere solvent reorganization energy.

Reorganization energies of diprotonated and saddle-distorted porphyrins in photoinduced electron-transfer reduction controlled by conformationaldistortion

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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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Oxidative purification of halogenated ferrocenes

We report the large scale syntheses and ‘oxidative purification’ of fcI2, fcBr2 and FcBr (fc = ferrocene-1,1?-diyl, Fc = ferrocenyl). These valuable starting materials are typically laborious to separate via conventional techniques, but can be readily isolated by taking advantage of their increased E1/2 relative to FcH/FcX contaminants. Our work extends this methodology towards a generic tool for the separation of redox active mixtures.

Oxidative purification of halogenated ferrocenes

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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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Ruthenium complexes with dendritic ferrocenyl phosphanes: Synthesis, characterization, and application in the catalytic redox isomerization of allylic alcohols

An efficient system for the catalytic redox isomerization of the allylic alcohol 1-octen-3-ol to 3-octanone is presented. The homogeneous ruthenium(II) catalyst contains a monodentate phosphane ligand with a ferrocene moiety in the backbone and provides 3-octanone in quantitative yields. The activity is increased by nearly 90 % with respect to the corresponding triphenyl phosphane ruthenium(II) complex. By grafting the catalyst at the surface of a dendrimer, the catalytic activity is further increased. By introducing different spacers between ferrocene and phosphorus, the influence on the electronic properties of the complexes is shown by evaluating the electrochemical behavior of the compounds.

Ruthenium complexes with dendritic ferrocenyl phosphanes: Synthesis, characterization, and application in the catalytic redox isomerization of allylic alcohols

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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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Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Various metalloligands and inorganic-organic hybrid bridging ligands have been incorporated in polynuclear complexes and bimetallic coordination polymers. Ferrocene, exhibiting redox activity and facile chemical modification, is a versatile metalloligand component. However, most metal complexes with ferrocene-containing ligands form discrete low-dimensional chelate complexes or coordination polymers. Thus, we designed and synthesized ferrocene-based multidentate ligands, 1,2-di(4-pyridylthio)ferrocene (L1) and 1,2-di(2-pyridylthio)ferrocene (L2). Here we report the synthesis and structures of molecular square complexes and coordination polymers containing L1, which reacted with M(hfac)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) and AgCF3SO3 to yield molecular square complexes [M(hfac)2(L1)]2¡¤2C6H5CH3 [M = Ni (1) and Co (2)] and [Ag(CF3SO3)(L1)(H2O)0.5]2¡¤2CH2Cl2¡¤H2O (3). The molecular square units comprise two metal ions bridged by two ligands. Isomorphic complexes 1 and 2 accommodate two toluene molecules above and below the molecular square. L1 reacted with Cu(hfac)2 and CuI to yield zigzag, {[Cu(hfac)2(L1)]}n¡¤0.25n(CH2Cl2) (4), and ribbon-shaped, {[Cu4I4(L1)2]}n (5), coordination polymers. In 4, L1 behaves as a bidentate N,N-ligand bridging the CuII ions, while in 5 it acts as a tridentate S,N,N-ligand linking the stepped-cubane Cu4I4 units. L1 reacted with AgX to form two-dimensional coordination polymers {[Ag(ClO4)(L1)]}n (6) and {[Ag(L1)]PF6}n (7), in which it acted as a tetradentate S,S,N,N-ligand. These complexes have topologies based on multidentate coordination of 1,2-substituted L1.

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

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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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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 | 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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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 | 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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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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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