The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

Baldoli, Clara; Cerea, P.; Falciola, L.; Giannini, Clelia; Licandro, Emanuela; Maiorana, Stefano; Mussini, Patrizia R.; Perdicchia, Dario

doi:10.1016/j.jorganchem.2005.07.048

Cited by 34 publications

(40 citation statements)

References 35 publications

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“…al. [60] and two aminocarbene complexes of tungsten reported by Ludvík [61]. The second oxidation process observed involves the two-electron oxidation of the electrochemically generated W(II) centre to W(IV), indicated with peak (c) in Figure 5.…”

Section: Electrochemical Oxidationmentioning

confidence: 82%

“…al. [60], who also suggested a two-electron metal-based oxidation process for the first oxidation, observed for a series of five alkoxy-, amino-and hydrazinocarbene complexes of tungsten. The two-electron stoichiometry of the irreversible W(0) carbene oxidation is in contrast with the reversible one-electron oxidation observed for pentacarbonyl Cr(0) carbenes [1,3,60].…”

Section: And Dft Calculationsmentioning

confidence: 97%

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Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes

Landman

Pretorius

Fraser

et al. 2014

Electrochimica Acta

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Dedicated to the memory of Professor Robert Vleggaar is investigated by means of cyclic voltammetry. The complexes all exhibit a twoelectron oxidation process that is W-based and a one-electron reduction that is mainly localized on the carbene ligand. Complexes 1-4 and 9-12 are considerably more difficult to oxidize than 5-8 due to the better π-acceptor ability of the (CO) 4 (PR' 3 ) (R' = Ph or OPh) ligand combination than that of (CO) 3 (dppe). Density functional theory calculations on the neutral, reduced and oxidized complexes confirmed the role of the frontier orbitals in the oxidation and reduction processes and enabled formulation of mathematical relationships that can be used to predict experimental measured potentials. X-ray crystal structures of 2cis, 3 and 5 are discussed.

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Section: Electrochemical Oxidationmentioning

confidence: 82%

Section: And Dft Calculationsmentioning

confidence: 97%

Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes

Landman

Pretorius

Fraser

et al. 2014

Electrochimica Acta

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“…the dppe-containing complexes [(CO) 3 [45,46,47,47,52]. Since the oxidation centre for all these Fischer Cr-carbene complexes is mainly located on the Cr-metal centre, it is expected that the electronic influence of the dppe ligand directly attached to the Cr atom will be more pronounced than the influence of the different substituents on the carbene ligand.…”

Section: Cr(o)-cr(i) Oxidationmentioning

confidence: 99%

Fac and mer dppe-substituted Fischer carbene complexes of chromium: X-ray, DFT and electrochemical study

Landman

Liu

Fraser

et al. 2014

Journal of Organometallic Chemistry

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“…al. 43 proposed that for tungsten-carbenes, the first electron oxidation immediately leads to the loss of a second electron, i.e. a two-electron oxidation process.…”

Section: · Chelate Vs Non-chelate (Compare 5 and 6 To 7 And 8)mentioning

confidence: 99%

“…al. 43 and two aminocarbene complexes of tungsten reported by Ludvík. 44 The reduction peak observed at potentials below 1500 mV vs. Fc/Fc + is localized on the carbene moiety according to Ludvík.…”

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confidence: 94%

Synthesis, Structure, and Electrochemistry of Fischer Alkoxy- and Aminocarbene Complexes of Tungsten: The Use of DFT To Predict and Understand Oxidation and Reduction Potentials

et al. 2013

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Reactions of Fischer alkoxycarbene complexes[W(CO) 5 {C(OEt)Ar}], Ar = thienyl (1) or furyl (2), with ethylene diamine lead to the formation of two different reaction products: an aminolysis product (5 or 6) where the ethoxy substituent of the carbene ligand is replaced by the ethylene diamine moiety, as well as a chelated product where aminolysis and substitution of one carbonyl ligand had taken place, yielding 7 or 8. Aminolysis of 1 and 2 with cyclohexyl amine (CHA) produced the aminocarbene complexes 3 (Ar = thienyl) and 4 (Ar = furyl). Complexes 1-8 are electrochemically investigated by means of cyclic voltammetry. The relative shifts in the oxidation and reduction potentials are discussed and related to density functional theory (DFT) calculated energies. DFT calculations further show that the oxidation center is located on the metal and the carbonyl groups, while the reduction center is localized on the carbene moiety and is strongly influenced by the electronic properties of its substituents. Crystal structures of 1-4, 6 and 8 are reported.

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The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

Cited by 34 publications

References 35 publications

Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes

Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes

Fac and mer dppe-substituted Fischer carbene complexes of chromium: X-ray, DFT and electrochemical study

Synthesis, Structure, and Electrochemistry of Fischer Alkoxy- and Aminocarbene Complexes of Tungsten: The Use of DFT To Predict and Understand Oxidation and Reduction Potentials

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