The effect of 19-electron formation constants on the electrochemistry and electron transfer induced substitution reactions of cyclopentadienylmetal halide complexes

Munisamy, Thiruvengadam; Gipson, Stephen L.

doi:10.1016/j.jorganchem.2006.11.003

Cited by 11 publications

(4 citation statements)

References 24 publications

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“…2) for each dimer pair (Fp 2 /Rp 2 vs. Mp 2 /Wp 2 ). The rate of cleavage of the dimer radical must be faster by >5 orders of magnitude to allow for a satisfactory simulated fit to the CV data for the Mp 2 /Wp 2 pair [32]. This is an entirely reasonable finding given the different nature of the bonding in these systems: metalemetal and CO bridging bonds vs. metalemetal only bonds (the trans and cis bridged isomers of Fp 2 /Rp 2 are not explicitly considered).…”

Section: Electrochemical Simulationmentioning

confidence: 62%

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

Donovan

Felton

2012

Journal of Organometallic Chemistry

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Section: Electrochemical Simulationmentioning

confidence: 62%

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

Donovan

Felton

2012

Journal of Organometallic Chemistry

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“…This redox behavior was deeply discussed by Munisamy et al 12 The iodide metal complex, MI (where M = [CpFe(CO) 2 ]), underwent a reduction to form the corresponding anion complex [MI] − at the corresponding peak A . The latter is a 19‐electron metal complex that releases iodide irreversibly as it quickly transforms into the neutral complex M. Then, at potential values that are close to the potential A , the complex M underwent a reduction, resulting in the monoanion M − .…”

Section: Resultsmentioning

confidence: 90%

New insights on the application of half‐sandwich complexes with metal–iodide bonds for agricultural fungicides

Corsini,

Fabrizi de Biani,

Policastro

et al. 2024

Applied Organom Chemis

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Cyclopentadienyl half‐sandwich complexes of cobalt and iron with metal–iodide bonds were reported to efficiently inhibit the growth of phytopathogenic fungi. With the aim of investigating the structure/activity relationships, further in vitro experiments were carried out. Cyclic voltammetric characterization, chemical stability, and antiradical activity were performed in two solvents: dimethyl sulfoxide and acetone. The iodide ion removal from the complex appears to be the key point of antifungal activity. Moreover, a preliminary cell viability test on human keratinocytes was also assessed in order to verify the nontoxic effect of tested compounds. The cytotoxicity for all the complexes was comparable with that shown by povidone iodide, a common antifungal agent recognized as safe (IC50 > 300 mM). Furthermore, the work proposes an additional roadmap (sequence of experiments) at the initial antifungal activity tests, which improves insight into their mechanism of action.

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“…However, the complexes containing halides ( 3 − 10 ) show additional irreversible oxidation peaks, presumably originating from oxidation of the dissociated halide ions. It is noted that bromide- and chloride-containing species showed one additional peak, but iodide-containing complexes ( 3 , 4 , 7 , and 10 ) showed two additional peaks, reminiscent of the two-step oxidation of iodide to triiodide and then iodine typically observed in nonaqueous solvents . The electrochemical parameters are listed in Table .…”

Section: Resultsmentioning

confidence: 99%

“…It is noted that bromide-and chloridecontaining species showed one additional peak, but iodide-containing complexes (3, 4, 7, and 10) showed two additional peaks, reminiscent of the two-step oxidation of iodide to triiodide and then iodine typically observed in nonaqueous solvents. 34 The electrochemical parameters are listed in Table 6. We have found some solid residue after the experiments, which suggests decomposition of the compounds during the redox process.…”

Section: Resultsmentioning

confidence: 99%

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Sarkar¹,

Wen²,

Wang³

et al. 2009

Inorg. Chem.

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Reactions of perchlorate salts of Hg(II)/Cd(II) with [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] (denoted as L) produced dicationic clusters [HgL(2)](ClO(4))(2), 1; [HgL(3)](ClO(4))(2), 2; and [CdL(3)(H(2)O)](ClO(4))(2), 11. However, the reactions of L with Hg(II)/Cd(II) halides yielded neutral complexes. For instance, HgI(2) produced [Hg(3)I(6)L(2)], 3, or [HgI(2)L(2)], 4, depending on the metal-to-ligand ratio used. Reaction of L with any of the Hg(II)/Cd(II) halides in a 1:1 ratio produced neutral clusters [HgX(mu-X)L](2) (M = Hg; X = Cl, 5; Br, 6; I, 7; M = Cd; X = Cl, 8; Br, 9; I, 10). Thus, variation of the M-to-L ratio made it possible for the formation of compounds with different metal/ligand stoichiometries only when ClO(4)(-) and I(-) salts of Hg(II) were used. Single-crystal X-ray crystallography revealed that two and three L units were connected to a Hg(II) via its Se atom in 1 and 2, respectively, whereas Hg(II) in 4 was connected to two "I" and two "L" units. An L (through its Se) and a terminal halogen were attached to each of the Hg(II)'s of the Hg(2)X(2) parallelogram core in 5 and 6. The cadmium complex 8, with a Cd(2)Cl(2) parallelogram core, was isostructural with the mercury complex 5. Although bonding and connectivity in 8 were similar to those in 9 and 10, the conformation of the bulky L ligands was unusually syn in 9 and 10, unlike the anti orientation in 5, 6, and 8. The syn conformation of L was also observed in compounds 1 and 2. Secondary interactions, namely, Se...Se interaction, the X...H-C type of H-bonding (X = halogen or Se), and pi-stacking, revealed in the structures played a role in determining the ligand conformation. The [P(Se)(O(i)Pr)(2)](-), the conjugate base of secondary phosphine selenide [HP(Se)(O(i)Pr)(2)], acted as a bridge with P bonded to Fe and Se bonded to Hg (or Cd) in these heterometallic clusters. Compound 5 further demonstrated a longer P-Se bond in the secondary phosphine selenide compared to that in isostructural, tertiary phosphine selenide metal complexes.

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The effect of 19-electron formation constants on the electrochemistry and electron transfer induced substitution reactions of cyclopentadienylmetal halide complexes

Cited by 11 publications

References 24 publications

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

New insights on the application of half‐sandwich complexes with metal–iodide bonds for agricultural fungicides

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

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The effect of 19-electron formation constants on the electrochemistry and electron transfer induced substitution reactions of cyclopentadienylmetal halide complexes

Cited by 11 publications

References 24 publications

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

New insights on the application of half‐sandwich complexes with metal–iodide bonds for agricultural fungicides

Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OiPr)2]−as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

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Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes