The Electronic Structure of the Vanadyl Ion

Ballhausen, C. J.; Gray, Harry B.

doi:10.1021/ic50001a022

Cited by 1,432 publications

(593 citation statements)

References 2 publications

Supporting

Mentioning

515

Contrasting

Unclassified

Order By: Relevance

“…This is the second (after the Cu(II) complex) well-studied complex of transition metal ions in aqueous solutions. It was reported that the vanadyl ion surrounded by four nitrogen atoms in different frozen solutions did not show any shfs from the 14 N either [15], which corresponded to the suggested scheme of energy levels [27]. Studies of vanadyl porphyrins in different solutions are scarce, which explains that the shfs on the 14 N nuclei is still an open question.…”

Section: Resultsmentioning

confidence: 90%

“…1 ) in the substituent in the pyrrole ring (EP I, EP II) and methine bridge (TPP, Table 2), i.e., in the second coordination sphere of the vanadyl ion. Detailed analysis of the electronic structure of the vanadyl ion performed by Ballhausen and Gray [27] in the framework of the crystal field theory (MO LCAO) and then analysis of vanadyl porphyrin (MO LCAO) carried out by Kivelson and Lee [15] allowed the authors to explain the experimental parameters of the EPR and optical spectra. They suggested a scheme of the energy levels of s in the vanadyl porphyrin complex, which could be transformed according to the irreducible representations of 4v symmetry.…”

Section: Materials and Proceduresmentioning

confidence: 99%

See 1 more Smart Citation

EPR spectra of V(IV) complexes and the structure of oil porphyrins

Gilinskaya

2008

J Struct Chem

View full text Add to dashboard Cite

For natural bitumoids, the effects of the structure of vanadyl-porphyrin complexes on the EPR spectra were investigated. The ambiguity of the hyperfine structure (its presence or absence) corresponding to four nitrogen atoms in the spectra of oil vanadyl porphyrins correlates with the changes in the second coordination sphere of the nearest environment of the metal ion, namely, in methine bridges.

show abstract

Section: Resultsmentioning

confidence: 90%

Section: Materials and Proceduresmentioning

confidence: 99%

EPR spectra of V(IV) complexes and the structure of oil porphyrins

Gilinskaya

2008

J Struct Chem

View full text Add to dashboard Cite

show abstract

“…According to the molecular orbital scheme for [VO(H 2 O) 5 ] 2+ , this transition can be ascribed to the promotion of the single electron from the d xy orbital to the d yz or d xz orbital. 27 Valek et al showed that this degeneracy is lifted in less symmetrical complexes with the d yz orbital being lower in energy. 28 The d xy f d xz transition at approximately 600 nm is not well-resolved but is visible as a shoulder on the d xy f d x 2 -y 2 transition at 540 nm.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of O,N-Chelated Vanadium(IV) Oxo Phenolate Complexes: Electronic Effect of Meta and Para Substituents on the Vanadium Center

Koten¹,

Hagen²,

Barbon³

et al. 1999

Inorg. Chem.

View full text Add to dashboard Cite

A series of O,N-chelated vanadium(IV) oxo bis(phenolate) complexes (1a-i) have been prepared from [VOCl 2 -(THF) 2 ] and several ortho-amino-functionalized phenols in the presence of a base. The intermediates in the synthesis of these compounds are mono(phenolato)vanadate complexes, as was shown by the reaction of [VOCl 2 (THF) 2 ] with 1 equiv of HOC 6 H 2 (CH 2 NMe 2 ) 2 -2,6-Me-4 in the absence of base. This yielded [VOCl 2 (OC 6 H 2 (CH 2 NMe 2 )-2-Me-4-(CH 2 NHMe 2 )-6)] (2), in which the second amine function acts as an internal base, assisting in binding the formed equivalent of HCl. Complex 2 exists in the solid state as the dichlorovanadate(IV) species with the protonated amine function forming a three-centered intramolecular hydrogen bridge in which both a chloride atom and the oxygen atom of the phenolate ligand participate. EPR, UV-vis, and cyclic voltammetry analysis of the complexes with meta or para substituents (1a-g) on the aryloxy ring showed the hyperfine coupling constant, the HOMO-LUMO transition, and the oxidation potential, respectively, to be linearly related to the Hammett σ constants of the substituents on the monoanionic aryloxy ring. The oxidation potential shows a large dependence (dE ox /dσ ) 170 mV (per phenoxy ligand)) on the Hammett constant. Crystal data: 1a, orthorombic, Pbca, a ) 9.4321 (7)

show abstract

“…In a tetragonal crystal field (C 4v ), the 2 T 2 level splits into 2 B 2 and 2 E and 2 E splits into 2 B 1 and 2 A 1 . Thus for V 4 þ ion in tetragonal symmetry, one can expect three bands corresponding to the 2 B 2 -2 E, 2 B 2 -2 B 1 and 2 B 2 -2 A 1 transitions [34,35]. The general ordering of these energy levels is as follows: …”

Section: Optical Absorptionmentioning

confidence: 99%

Optical, physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Lakshmikantha

Ayachit

Anavekar

2014

Journal of Physics and Chemistry of Solids

View full text Add to dashboard Cite

a b s t r a c tGlasses in the compositions (Li 2 O) 25 -(BaO) 25 -(P 2 O 5 ) 50 À x -(V 2 O 5 ) x (with x ¼0.5,1.0,1.5,2.0,2.5, and 3.0 mol %) have been prepared by the conventional melt quenching technique. X-ray powder diffractrogram show broad peaks which conforms glassy nature of the sample. Differential scanning calorimetry (DSC) thermograms show characteristic glass transition temperature (T g ) and it increases with increasing substitution of V 2 O 5 for P 2 O 5 . The measured physical parameters like density, refractive index, ionic concentration and electronic polarizability are found to vary linearly with increasing x. Infrared spectra exhibits few bands, which are attributed to (P ¼O) AS , (P¼ O) S , (V¼O), (P-O-P) AS ,P-O-V, (P-O-P) AS and O-P-O vibrations. The optical absorption spectra of VO 2 þ ions in these glasses show three bands and are assigned to the 2 B 2 -2 E, 2 B 2 -2 B 1 and 2 B 2 -2 A 1 transitions. Electron paramagnetic resonance spectra of all the glass samples exhibit resonance signals characteristic of VO 2 þ ions. The values of SpinHamiltonian parameters indicate that the VO 2 þ ions are present in octahedral sites with tetragonal compression and belong to C 4V symmetry.

show abstract

The Electronic Structure of the Vanadyl Ion

Cited by 1,432 publications

References 2 publications

EPR spectra of V(IV) complexes and the structure of oil porphyrins

EPR spectra of V(IV) complexes and the structure of oil porphyrins

Synthesis and Characterization of O,N-Chelated Vanadium(IV) Oxo Phenolate Complexes: Electronic Effect of Meta and Para Substituents on the Vanadium Center

Optical, physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Contact Info

Product

Resources

About