Electrochemistry of Fe(CO)2(η5-C5H5)X-series. I. Detailed mechanism of reduction of [Fe(CO)2(η5-C5H5)]2 and [Fe(CO)2(η5-C5H5)]2Hg

Miholová, D.; Vlček, Antonı́n

doi:10.1016/s0020-1693(00)88440-6

Cited by 30 publications

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“…For example, the organoborane triple-decker sandwich complex [Ru 2 (η-arene) 2 (Et 2 C 2 B 3 H 3 )] (E°′ ) -0.34 V) was first oxidized with [FeCp 2 ] + (E°′ ) 0.0 V); the monocationic complex [Ru 2 (η-arene) 2 (Et 2 C 2 B 3 H 3 )] + was spectroscopically characterized and then reduced The anion is a strong one-electron reductant, but it has not been widely used. An anodic wave was reported at E 1/2 ) -1.74 V in THF at a mercury electrode, 448 but since the product of the oxidation was [Hg{Fe(CO) 2 Cp} 2 ] this potential is only an approximation of that for the reaction in eq 36. Another estimate of the formal potential associated with eq 36 (E°′ ) -1.84 V) was obtained by means of elegant redox equilibration studies.…”

Section: (Nme 2 )mentioning

confidence: 99%

“…The diiron complex (Fp 2 ) in eq 36 undergoes an irreversible reduction at ca. -2.0 V. 448,450 Solutions of Fpare prepared by reacting Fp 2 with strong reducing agents such as M/Hg or Na/K in ethers 451 (Fpreacts rapidly with alkyl halides and other electrophiles 452,453 ). Its solutions have been used in situ to reduce 18-electron cationic Mo(II) alkyne complexes, thereby initiating ligand coupling reactions.…”

Section: (Nme 2 )mentioning

confidence: 99%

“…The anion is a strong one-electron reductant, but it has not been widely used. An anodic wave was reported at E 1/2 = −1.74 V in THF at a mercury electrode, but since the product of the oxidation was [Hg{Fe(CO) 2 Cp} 2 ] this potential is only an approximation of that for the reaction in eq 36. Another estimate of the formal potential associated with eq 36 ( E °‘ = −1.84 V) was obtained by means of elegant redox equilibration studies .…”

Section: Metal Carbonylatesmentioning

confidence: 99%

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Chemical Redox Agents for Organometallic Chemistry

1996

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Section: (Nme 2 )mentioning

confidence: 99%

Section: (Nme 2 )mentioning

confidence: 99%

Section: Metal Carbonylatesmentioning

confidence: 99%

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Chemical Redox Agents for Organometallic Chemistry

1996

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“…The final mechanism to be considered, shown in Scheme III (eqs [16][17][18], is an EEC mechanism. In this sequence, an initial electron-transfer step generates the polynuclear radical-cation intermediate; this step is followed by a second electron transfer prior to the cleavage of a tin-metal bond.…”

Section: Wavenumbermentioning

confidence: 99%

Electrochemistry and infrared spectroelectrochemistry of MnSnPh4-n (M = CpMo(CO)3, Mn(CO)5, CpFe(CO)2; n = 1, 2)

Bullock¹,

Palazzotto²,

Mann

1990

Inorg. Chem.

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The electrochemistry and infrared spectroelectrochemistry of the series M"SnPh4_" (M = CpMo(CO)3, Mn(CO)s and CpFe(CO)2; = 1,2) and the corresponding homobinuclear compounds (M2) were examined in CH3CN/TBAH solutions (TBAH = tetra-M-butylammonium hexafiuorophosphate). Cyclic voltammetric and double-potential step chroncoulometric data indicate that all of these compounds undergo net two-electron oxidations, with concomitant metal-tin or, in the case of the homobinuclear species, metal-metal bond rupture. The oxidation products for the triphenyltin adducts are the solvent adducts of the transition-metal cation and the triphenyltin cation. For Mn(CO)5SnPh3, the oxidation process is chemically reversible. Oxidation of the diphenyltin-bridged compounds results in cleavage of only one metal-tin bond, to give the metal cation and a base-stabilized stannylene cation. An ECE mechanism is proposed for the oxidation of these species. [Mn(CO)5]3SnPh undergoes metal-tin bond cleavage reactions. The reductions of the compounds in this series and the homobinuclear compounds were also studied. Almost all of the reductions were net two-electron processes, which, like the oxidations, resulted in metal-tin or metal-metal bond cleavage. The reduction products for the homobinuclear species"were the monomeric metal anions. The triphenyltin adducts yielded the metal anions and either the triphenylstannate anion or the triphenyltin dimer species, Sn2Ph6, upon reduction, depending on the transition-metal moiety. The diphenyltin-bridged compounds were reduced to the transition-metal anions and an unreduced tin product, possibly an oligomerization product of diphenyltin. Infrared spectral data imply that this reduction proceeds via a terminal diphenylstannate anion adduct of the transition-metal moiety.

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“…2 Miholová and Vlcek later studied the reduction process in detail and reported that it occurs via an ECE mechanism involving an initial diffusion-controlled electron transfer. 3 The electrochemical oxidation of [CpFe(CO)2]2 has also been studied. In 1971, Meyer and co-workers published a report that discussed the electrooxidation of [CpFe(CO)2]2 in a variety of solvents.4 567It was found that in coordinating solvents, e.g., acetonitrile, the oxidation proceeds by two electrons and yields the monomeric metal-solvent adduct cation (eq 1).…”

Section: Introductionmentioning

confidence: 99%