Electrochemical and X‐ray Structural Aspects of Transition Metal Complexes Containing Redox‐Active Ferrocene Ligands

Zanello, Piero

doi:10.1002/9783527615599.ch07

Cited by 7 publications

(6 citation statements)

References 219 publications

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“…The electrochemical behaviour of the two half-units Each of the four compounds displays one chemically reversible redox process due to the monoelectronic oxidation of the ferrocenyl moiety, 57 with current ratio i pa /i pc equal to unity. The redox potentials of the four compounds are anodically shifted by 70-270 mV with respect to free ferrocene under the same electrochemical conditions (Table 3), clearly illustrating the electron withdrawing effect of the Schiff base side chain substituent.…”

Section: Njc Papermentioning

confidence: 99%

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

et al. 2022

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Section: Njc Papermentioning

confidence: 99%

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

et al. 2022

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“…The Fe(II) state is orange whereas Fe(III) (the ferrocenium ion) has a characteristic blue color. The electronic properties of ferrocene are acutely sensitive to functional groups attached to the Cp ring (Figure 3.1) [111–114]. …”

Section: Redox Species Used For Electrochemical Determination Of Kmentioning

confidence: 99%

Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

530

492

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Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redoxactivated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C 60 ). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.

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“…By simple 18-electron rule argument, we surmised that X-type coordination of a triplet nitrene ligand to the 17-electron ferrocenium [Cp 2 Fe(III)] + can be formulated as Fe(IV)-amidyl radical species, which would be reactive toward C–H amidation reactions (Scheme a). Ferrocenes are well-known for electron-transfer catalysis; however, their activity to mediate nitrene transfer to hydrocarbons is unprecedented . Here, we present that the [Cp 2 Fe(III)] + complex serves as an effective catalyst for intramolecular electrophilic amidyl radical addition to arenes to form 3,4-dihydroquinolin-2(1 H )-ones.…”

Section: Introductionmentioning

confidence: 90%

Intramolecular Arene C(sp²)–H Amidation Enabled by Ferrocenium-Mediated Decomposition of 1,4,2-Dioxazol-5-ones as Amidyl Radical Precursors

Sun,

Au,

Wong

et al. 2023

ACS Catal.

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Direct arene C−H functionalization by amidyl radicals for arylamides synthesis has made significant advances. While photocatalytic protocols can offer easy generation of amidyl radicals under mild conditions, designing catalysts involving earthabundant Fe complexes for C−H amidation is an attractive approach to bring about ligand-enabled selectivity control. However, due to preference for high-spin configuration, designing robust Fe catalysts for C−H amidation remains a substantial challenge. Taking the advantage of the strong Cp−Fe linkages, here we developed the 17-electron ferrocenium complexes as effective catalysts for facile intramolecular aryl C−H amidation with 1,4,2-dioxazol-5-one as amidyl radical precursors. The ferrocenium-catalyzed reaction affords 3,4-dihydroquinolin-2(1H)-ones in excellent yields and selectivity. Our experimental and computational studies revealed that the intramolecular arene amidation is brought about by electrophilic arene addition by reactive Fe(IV)-amidyl radical species. Consistent with the experimental findings, the regioselectivity (ipso-versus ortho-amidyl radical addition) is influenced by electronic factors. The ipso amidyl radical addition should form an azaspirocyclohexadienyl radical intermediate. Subsequent radical-polar crossover and 1,2-alkyl migration followed by rearomatization afforded the skeletal rearranged dihydroquinolinone lactams. A recyclable heterogeneous amidation catalyst has been prepared by grafting ferrocene onto commercially available silica, and comparable catalytic activities with the homogeneous system were observed.

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Electrochemical and X‐ray Structural Aspects of Transition Metal Complexes Containing Redox‐Active Ferrocene Ligands

Cited by 7 publications

References 219 publications

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

Electrochemistry of redox-active self-assembled monolayers

Intramolecular Arene C(sp²)–H Amidation Enabled by Ferrocenium-Mediated Decomposition of 1,4,2-Dioxazol-5-ones as Amidyl Radical Precursors

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Electrochemical and X‐ray Structural Aspects of Transition Metal Complexes Containing Redox‐Active Ferrocene Ligands

Cited by 7 publications

References 219 publications

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(ii) and Pd(ii) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

Electrochemistry of redox-active self-assembled monolayers

Intramolecular Arene C(sp2)–H Amidation Enabled by Ferrocenium-Mediated Decomposition of 1,4,2-Dioxazol-5-ones as Amidyl Radical Precursors

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Intramolecular Arene C(sp²)–H Amidation Enabled by Ferrocenium-Mediated Decomposition of 1,4,2-Dioxazol-5-ones as Amidyl Radical Precursors