1 3
Theor Chem Acc (2015) 134:116
DOI 10.1007/s00214-015-1719-2
REGULAR ARTICLE
Structural and spectral properties of tartrato complexes
of vanadium(V) from quantum chemical calculations
Gabriela Orešková
1 · Lukáš Krivosudský
1 · Ján Šimunek
1 · Jozef Noga
1,2,3
Received: 30 June 2015 / Accepted: 1 September 2015 / Published online: 16 September 2015
© Springer-Verlag Berlin Heidelberg 2015
calculated spectral properties were compared with experimental data.
Keywords Vanadium(V) complexes · Tartrato ligand ·
DFT calculations · Spectral properties · Chirality
1 Introduction
Transition metals complexes of tartaric acid have been the
subject of research in all the main areas of practical applications of chirality: biochemistry and medicinal chemistry [ 1 ], asymmetric catalysis [ 2 – 4 ], and chiral separations [ 5 – 9 ]. It is not surprising that the rapid development
of the chemistry of vanadium in recent decades smoothly
covered all of these areas by itself. The main attention has
been devoted to the insulin-mimetic activity of vanadium
complexes of tartaric acid [ 10 , 11 ]. Chirality of some insulinomimetic dinuclear vanadyl(IV)–tartrate complexes has
been considered as well, resulting in an interesting fi nding
that both the complexes of naturally occurring L -tartaric
acid and racemic tartaric acid are highly active [ 12 ].
The catalytic activity of the VO(stearate) 2 – L / D tartrate system with the suggested presence of a dinuclear
oxidovanadium(IV) tartrato complex leads to an enantioselective oxidative coupling polymerization of 2,3-dihydroxynaphthalene [ 13 ]. Very recently, the second harmonic generation and spin-dimer behavior were observed
for oxovanadium(IV) tartrates [ 14 ]. In addition, a study
appeared on an interaction of tartratovanadates with chiral
Fe(II) and Ni(II) tris(2,2′-bipyridine) complexes manifesting itself with the solid state by packing into homochiral
layers in the crystal structure [ 15 ].
The following dinuclear and tetranuclear tartrato
complexes of vanadium(V) previously isolated from
Abstract Structural and spectral properties of three complex anions of vanadium(V) with tartrato ligands were theoretically studied by all-electron DFT calculations employing various functionals, such as BP86, BLYP, B3LYP,
BHHLYP, and the M06-family. Results were statistically
evaluated, with the aim to fi nd a reliable, fairly accurate,
and yet computationally effi cient combination of methods and basis sets to be used in computational chemistry
of vanadium(V) complex anions at even larger scale. Subsequent vibrational analysis based upon BP86 and B3LYP
data provided a fair agreement with the experimental vibrational spectra. Additionally, the absorption UV–Vis and the
electronic circular dichroism spectra of studied compounds
were simulated via time-dependent density functional theory calculations with the long-range corrected functionals (CAM-B3LYP, LC- ω PBE, and ω B97XD). Finally, the
51
V NMR chemical shifts were calculated using the GIAO
approach at the B3PW91 level. The solvent effect was
simulated within the PCM model. Where available, the
Published as part of the special collection of articles “Festschrift
in honour of P. R. Surjan”.
Electronic supplementary material The online version of this
article (doi: 10.1007/s00214-015-1719-2 ) contains supplementary
material, which is available to authorized users.
* Jozef Noga
jozef.noga@fns.uniba.sk
1
Department of Inorganic Chemistry, Faculty of Natural
Sciences , Comenius University , Ilkovi c ˇ ova 6 ,
84215 Bratislava , Slovakia
2
Institute of Inorganic Chemistry , Slovak Academy
of Sciences , Dúbravská cesta 9 , 84536 Bratislava , Slovakia
3
Computing Centre , Slovak Academy of Sciences , Dúbravská
cesta 9 , 84535 Bratislava , Slovakia
123
Reprinted from the journal
Theor Chem Acc (2015) 134:116
DOI 10.1007/s00214-015-1719-2
REGULAR ARTICLE
Structural and spectral properties of tartrato complexes
of vanadium(V) from quantum chemical calculations
Gabriela Orešková
1 · Lukáš Krivosudský
1 · Ján Šimunek
1 · Jozef Noga
1,2,3
Received: 30 June 2015 / Accepted: 1 September 2015 / Published online: 16 September 2015
© Springer-Verlag Berlin Heidelberg 2015
calculated spectral properties were compared with experimental data.
Keywords Vanadium(V) complexes · Tartrato ligand ·
DFT calculations · Spectral properties · Chirality
1 Introduction
Transition metals complexes of tartaric acid have been the
subject of research in all the main areas of practical applications of chirality: biochemistry and medicinal chemistry [ 1 ], asymmetric catalysis [ 2 – 4 ], and chiral separations [ 5 – 9 ]. It is not surprising that the rapid development
of the chemistry of vanadium in recent decades smoothly
covered all of these areas by itself. The main attention has
been devoted to the insulin-mimetic activity of vanadium
complexes of tartaric acid [ 10 , 11 ]. Chirality of some insulinomimetic dinuclear vanadyl(IV)–tartrate complexes has
been considered as well, resulting in an interesting fi nding
that both the complexes of naturally occurring L -tartaric
acid and racemic tartaric acid are highly active [ 12 ].
The catalytic activity of the VO(stearate) 2 – L / D tartrate system with the suggested presence of a dinuclear
oxidovanadium(IV) tartrato complex leads to an enantioselective oxidative coupling polymerization of 2,3-dihydroxynaphthalene [ 13 ]. Very recently, the second harmonic generation and spin-dimer behavior were observed
for oxovanadium(IV) tartrates [ 14 ]. In addition, a study
appeared on an interaction of tartratovanadates with chiral
Fe(II) and Ni(II) tris(2,2′-bipyridine) complexes manifesting itself with the solid state by packing into homochiral
layers in the crystal structure [ 15 ].
The following dinuclear and tetranuclear tartrato
complexes of vanadium(V) previously isolated from
Abstract Structural and spectral properties of three complex anions of vanadium(V) with tartrato ligands were theoretically studied by all-electron DFT calculations employing various functionals, such as BP86, BLYP, B3LYP,
BHHLYP, and the M06-family. Results were statistically
evaluated, with the aim to fi nd a reliable, fairly accurate,
and yet computationally effi cient combination of methods and basis sets to be used in computational chemistry
of vanadium(V) complex anions at even larger scale. Subsequent vibrational analysis based upon BP86 and B3LYP
data provided a fair agreement with the experimental vibrational spectra. Additionally, the absorption UV–Vis and the
electronic circular dichroism spectra of studied compounds
were simulated via time-dependent density functional theory calculations with the long-range corrected functionals (CAM-B3LYP, LC- ω PBE, and ω B97XD). Finally, the
51
V NMR chemical shifts were calculated using the GIAO
approach at the B3PW91 level. The solvent effect was
simulated within the PCM model. Where available, the
Published as part of the special collection of articles “Festschrift
in honour of P. R. Surjan”.
Electronic supplementary material The online version of this
article (doi: 10.1007/s00214-015-1719-2 ) contains supplementary
material, which is available to authorized users.
* Jozef Noga
jozef.noga@fns.uniba.sk
1
Department of Inorganic Chemistry, Faculty of Natural
Sciences , Comenius University , Ilkovi c ˇ ova 6 ,
84215 Bratislava , Slovakia
2
Institute of Inorganic Chemistry , Slovak Academy
of Sciences , Dúbravská cesta 9 , 84536 Bratislava , Slovakia
3
Computing Centre , Slovak Academy of Sciences , Dúbravská
cesta 9 , 84535 Bratislava , Slovakia
123
Reprinted from the journal