title: Versatile Reactivity and Theoretical Evaluation of Mono- and Dinuclear Oxidovanadium(V) Compounds of Aroylazines: Electrogeneration of Mixed-Valence Divanadium(IV,V) Complexes.
abstract: The substituted hydrazones H2L(1-4) (L(1-4) = dibasic tridentate ONO(2-) donor ligands) obtained by the condensation of 2-hydroxy-1-naphthaldehyde and 2-aminobenzoylhydrazine (H2hnal-abhz) (H2L(1)) , 2-hydroxy-1-naphthaldehyde and 2-hydroxybenzoylhydrazine (H2hnal-hbhz) (H2L(2)), 2-hydroxy-1-acetonaphthone and benzoylhydrazine (H2han-bhz) (H2L(3)), or 2-hydroxy-1-acetonaphthone and 2-aminobenzoylhydrazine (H2han-abhz) (H2L(4)) are prepared and characterized. Reaction of ammonium vanadate with the appropriate H2L(1-4) results in the formation of oxidoethoxidovanadium(V) [V(V)O(OEt)(L(1-4))] (1-4) complexes. All compounds are characterized in the solid state and in solution by spectroscopic techniques (IR, UV-vis, (1)H, (13)C, and (51)V NMR, and electrospray ionization mass spectrometry). Single-crystal X-ray diffraction analysis of 1, 3, and 4 confirms the coordination of the corresponding ligands in the dianionic (ONO(2-)) enolate tautomeric form. In solution, the structurally characterized [V(V)O(OEt)(L)] compounds transform into the monooxido-bridged divanadium(V,V) [(V(V)OL)2-μ-O] complexes, with the processes being studied by IR and (1)H, (13)C, and (51)V NMR. The density functional theory (DFT) calculated Gibbs free energy of reaction 2[V(V)O(OEt)(L(4))] + H2O ⇆ [(V(V)OL(4))2-μ-O] + 2EtOH is only 2-3 kcal mol(-1), indicating that the dinuclear complexes may form in a significant amount. The electrochemical behavior of the complexes is investigated by cyclic voltammetry, with the V(V)-V(IV) E1/2(red) values being in the range 0.27-0.44 V (vs SCE). Upon controlled potential electrolysis, the corresponding (L)(O)V(IV)-O-V(V)(O)(L) mixed-valence species are obtained upon partial reduction of the [(V(V)OL)2-μ-O] complexes formed in solution, and some spectroscopic characteristics of these dinuclear mixed-valence complexes are investigated using DFT calculations and by electron paramagnetic resonance (EPR), with the formation of V(IV)-O-V(V) species being confirmed by the observation of a 15-line pattern in the EPR spectra at room temperature.
authors.affiliation: Department of Chemistry, National Institute of Technology , Rourkela 769008, Odisha, India.|Department of Chemistry, Indira Gandhi Institute of Technology , Sarang, Parjang, Dhenkanal 759146, India.
authors.forename: Subhashree P
authors.initials: SP
authors.lastname: Dash
authors.affiliation: Department of Chemistry, National Institute of Technology , Rourkela 769008, Odisha, India.
authors.forename: Satabdi
authors.initials: S
authors.lastname: Roy
authors.affiliation: Department of Chemistry, National Institute of Technology , Rourkela 769008, Odisha, India.
authors.forename: Monalisa
authors.initials: M
authors.lastname: Mohanty
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa , Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.
authors.forename: M Fernanda N N
authors.initials: MF
authors.lastname: Carvalho
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa , Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.
authors.forename: Maxim L
authors.initials: ML
authors.lastname: Kuznetsov
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa , Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.
authors.forename: João Costa
authors.initials: JC
authors.lastname: Pessoa
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa , Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.|Centre for Nano and Material Sciences, Jain University , Jain Global Campus, Jakkasandra Post, Bangalore 562112, India.
authors.forename: Amit
authors.initials: A
authors.lastname: Kumar
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science , Bangalore 560012, India.
authors.forename: Yogesh P
authors.initials: YP
authors.lastname: Patil
authors.affiliation: Department of Chemistry, Fribourg Center for Nanomaterials, University of Fribourg , CH-1700 Fribourg, Switzerland.
authors.forename: Aurélien
authors.initials: A
authors.lastname: Crochet
authors.affiliation: Department of Chemistry, National Institute of Technology , Rourkela 769008, Odisha, India.
authors.forename: Rupam
authors.initials: R
authors.lastname: Dinda