Polarographic behavior of bis(.pi.-cyclopentadienyl)-N,N-dialkyldithiocarbamatovanadium(IV) tetraphenylborates in acetone. Example of an ECEC mechanism

Bond, Alan M.; Casey, A. T.; Thackeray, J. R.

doi:10.1021/ic50122a036

Cited by 33 publications

(14 citation statements)

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“…Electrochemistry. Although extensive heterogeneous electron-transfer properties have been documented for Cp 2 VCl 2 − and its related analogues, there is very little information available on the chelated vanadocene(IV) complexes. , Cyclic voltammetric studies of 1 and 2 in acetonitrile show that both complexes undergo identical electron-transfer processes over the potential range +2.1 to −2.5 V (vs the Cp 2 Fe +/0 couple). As illustrated in Figure and Table , each complex displays one reversible couple, centered at −0.62 V, attributable to the V III/IV redox process.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of Bis(π-cyclopentadienyl)vanadium(IV) 1,10-Phenanthroline and 2,2‘-Bipyridine Compounds and Their Interactions with Artificial Membranes

et al. 1999

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The reaction of in situ generated Cp(2)V(OTf)(2) (Cp = cyclopentadienyl; OTf = O(3)SCF(3)) with excess 1,10-phenanthroline and 2,2'-bipyridine yields the d(1) vanadocene coordination compounds [Cp(2)V(phen)][OTf](2) (1) and [Cp(2)V(bpy)][OTf](2) (2), respectively. The compounds have been characterized by UV-vis and EPR spectroscopy and by cyclic voltammetry. The complexes have relatively low vanadium(IV)-vanadium(III) reduction potentials (-0.62 V vs Cp(2)Fe(+/0) in acetonitrile). Structures of 1 and 2 have been determined by X-ray crystallography. Compound 1 crystallized in a monoclinic system, space group P2(1)/n, with a = 10.2763(5) Å, b = 18.1646(9) Å, c = 13.5741(7) Å, beta = 99.4150(10) degrees, and Z = 4. Refinement of its structure by full-matrix least-squares techniques gave final residuals R = 0.040 and R(w) = 0.096. Compound 2 crystallized in a monoclinic system, space group P2(1)/c, with a = 10.6451(6) Å, b = 18.3863(10) Å, c = 12.6993(7) Å, beta = 98.6220(10) degrees, and Z = 4. Refinement of its structure by full-matrix least-squares techniques gave final residuals R = 0.046 and R(w) = 0.101. The two nitrogen atoms and centroids of the two cyclopentadienyl rings for both compounds occupy a distorted tetrahedral geometry around the vanadium(IV) center. The chelated ring plane is inclined closer to one of the neighboring Cp rings with the tilt more evident in 1 ( approximately 8 degrees ) than 2 ( approximately 4 degrees ). The membrane interactions of these compounds and the titanium analogues, [Cp(2)Ti(phen)][OTf](2) (3) and [Cp(2)Ti(bpy)][OTf](2) (4), have been studied with zwitterionic unilamellar liposomes as artificial membranes. We show that the ability of metallocenes to enhance the permeability of a liposomal membrane depends on the hydrophobicity, as well as the size and planarity of the ancillary chelated ligands, but not the nature of the central metal ion. Also provided is evidence that metallocene-induced permeability changes in artificial membranes are not caused by lipid peroxidation.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of Bis(π-cyclopentadienyl)vanadium(IV) 1,10-Phenanthroline and 2,2‘-Bipyridine Compounds and Their Interactions with Artificial Membranes

et al. 1999

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“…Such processes have been noted for other dithiocarbamate complexes at the dropping mercury electrode. 31 In view of the rapidity with which mercury decomposes quite concentrated solutions of Fe(Et2dtc)3 (and also Fe((/-Pr)2dtc)3, Fe(Me2dtc)3, and presumably others), it would seem that polarographic analysis of ferric dithiocarbamates at a dropping mercury electrode (or simply in the presence of mercury and any O2) could be quite unreliable (cf. ref 32).…”

Section: Resultsmentioning

confidence: 99%

Tris(dithiocarbamato) complexes of iron(II), iron(III), and iron(IV). Electrochemical study

Chant¹,

Hendrickson²,

Martin³

et al. 1975

Inorg. Chem.

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“…It should be noted that the first theoretical and experimental description of the electroanalysis of an ECE b process was introduced in 1972 and focused upon the reduction of hexacyanochromate(III) in water. [10] This research led to the identification of further examples in the field of inorganic [11,26] and organic chemistry [8,12] in the ensuing years.…”

Section: Electroanalytical Investigationsmentioning

confidence: 99%

“…In these cases, an electrochemical step catalyzes an overall redox‐neutral chemical reaction, which is why these scenarios are referred to as “electrocatalyzed” or “electrochemically catalyzed” . While the underlying principles were originally described in the context of inorganic and organometallic chemistry, they were later successfully applied to organic reactions such as cycloadditions, nucleophilic aromatic substitutions, olefin isomerizations and a number of molecular rearrangements . The intent of this review is to discuss the fundamental aspects of such electrochemically catalyzed reactions, and to show the applications in organic electrochemistry from the early discoveries to the most recent developments.…”

Section: Introductionmentioning

confidence: 99%

Electrons and Holes as Catalysts in Organic Electrosynthesis

Francke

Little

2019

ChemElectroChem

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The injection (or removal) of electrons into (or from) a substrate by an electrode can effectively catalyze various redox‐neutral reactions that otherwise require harsh conditions and/or the use of reagents. Such processes involve the electrogeneration of an ionic or radical ionic species, which after a coupled chemical step either undergoes a backward electron exchange with the electrode (ECEb mechanism) or triggers a chain process in the bulk solution. Under these circumstances, sub‐stoichiometric amounts of charge are sufficient to achieve a full conversion and conceptionally, the electrons and holes can be understood as being catalysts. This principle has been successfully applied to accomplish a number of redox‐neutral transformations such as molecular rearrangements, Diels‐Alder‐type cycloadditions and radical substitution reactions (SRN1) in a mild and atom‐economical fashion. Although examples have been reported but sporadically since the early 1970s, a number of exciting recent developments have led us to review and discuss these cases using unifying mechanistic concepts that are described herein.

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Polarographic behavior of bis(.pi.-cyclopentadienyl)-N,N-dialkyldithiocarbamatovanadium(IV) tetraphenylborates in acetone. Example of an ECEC mechanism

Cited by 33 publications

References 0 publications

Synthesis and Structure of Bis(π-cyclopentadienyl)vanadium(IV) 1,10-Phenanthroline and 2,2‘-Bipyridine Compounds and Their Interactions with Artificial Membranes

Synthesis and Structure of Bis(π-cyclopentadienyl)vanadium(IV) 1,10-Phenanthroline and 2,2‘-Bipyridine Compounds and Their Interactions with Artificial Membranes

Tris(dithiocarbamato) complexes of iron(II), iron(III), and iron(IV). Electrochemical study

Electrons and Holes as Catalysts in Organic Electrosynthesis

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