DFT study of the V(IV)/V(V) oxidation mechanism in the presence of N-hydroxyacetamide

Noronha, Antonio Luiz Oliveira de; Duarte, Hélio A.

doi:10.1016/j.jinorgbio.2005.05.015

Cited by 8 publications

(1 citation statement)

References 53 publications

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“…A study of outer-sphere oxidation of I À by [H 6 Co III Mo 6 O 24 ] 3À has estimated the self exchange rate constant for the 6-molybdocobaltate(III)/(II) couple to be 3.5 M À1 s À1 . 18 Inner-sphere and electron and atom transfer DFT studies on oxidation of V(IV) to V(V) in aqueous acetohydroxamic acid suggests reaction of d OH, d OOH and H 2 O 2 with an intermediate formed by acetohydroxamic acid and V. 19 There was quite good agreement between experimental and theoretical results.…”

Section: Outer-sphere Electron Transfer and Self Exchange Reactionsmentioning

confidence: 81%

Mechanisms of reactions in solution

Davies

2006

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: Outer-sphere Electron Transfer and Self Exchange Reactionsmentioning

confidence: 81%

Mechanisms of reactions in solution

Davies

2006

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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DFT/PCM investigation of the Mn(II) chemical speciation in aqueous solution

Abreu

Guimarães

Duarte

2008

Int J of Quantum Chemistry

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Chemical speciation of Mn(II) in aqueous solution has been investigated by means of density functional methods. Different geometries and electronic states of all species arising from the Mn(II) hydrolysis have been calculated. The Gibbs free energy of the hydrolysis reaction and the respective equilibrium constants have been estimated and compared with the available experimental data. Polarizable continuum model (PCM-UAHF/6-31ϩG(d)) was used to estimate the solvation energy. The ionization potential of the predominant species are linearly dependent on the number of hydroxyls in their structure. The Mn(II)/Mn(III) oxidation potential estimate is in good agreement with the experimental value, about 0.2 V smaller. The estimated hydrolysis reaction energies are in good agreement with the experimental values with an error of about 3 kcal mol Ϫ1 (PBE/TZVP). The unique exception is the [Mn(OH) 3 ] Ϫ hydrolysis constant which is not in good agreement with the experimental value. This is attributed to inaccuracy of the presently available experimental value and the PCM solvation free energy estimate. The results shown in this work reinforce the importance of the chemical speciation in order to understand at a molecular level the mechanism of processes involving transition metal ions.

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DFT study of vanadyl (IV) complexes with low molecular mass ligands: Picolinate, oxalate, malonate, and maltolate

Rodrigues

Cunha

Silva

et al. 2011

Int J of Quantum Chemistry

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The insulin-mimetic activity of the VO 2þ complexes are much related to its chemical speciation in the blood serum. Low molecular mass ligands must have an important role in the mechanism of the VO 2þ biological activity affecting directly its absorption efficacy. In the present work, the chemical speciation of vanadyl (VO 2þ ) with malonate, maltolate, oxalate and picolinate ligands has been investigated by means of DFT/PCM calculations. Metal/Ligand 1:1 and 1:2 complexes have been calculated. All tautomers, conformations and the presence of water molecules acting as ligand fulfilling the coordination sphere of the metal center have been studied. The results showed that the 1:1 species prefer to have square pyramidal structure with two water molecules in the equatorial axis. The 1:2 species prefer the hexacoordinated structure with one water molecule in the available coordination site in the cis position with respect to the oxo group. The 6-membered ring malonate complex prefers to keep the square pyramidal structure without water molecule in the coordination sphere. The Gibbs free reaction energy for the formation of the 1:2 complexes from the interaction of the 1:1 complexes and the ligand was estimated. The error of the estimated values compared to the experimental data is not larger than 5 kcal mol À1 at the PBE/TZVP level of theory

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DFT study of the V(IV)/V(V) oxidation mechanism in the presence of N-hydroxyacetamide

Cited by 8 publications

References 53 publications

Mechanisms of reactions in solution

Mechanisms of reactions in solution

DFT/PCM investigation of the Mn(II) chemical speciation in aqueous solution

DFT study of vanadyl (IV) complexes with low molecular mass ligands: Picolinate, oxalate, malonate, and maltolate

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