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Formation in aqueous solution of a non-oxido VIV complex with VN6 coordination. Potentiometric, ESI-MS, spectroscopic and computational characterization.

Autorzy

Elżbieta Łodyga-Chruścińska

Agnieszka Szebesczyk

Daniele Sanna

Kaspar Hegetschweiler

Giovanni Micera

Eugenio Garribba

Rok wydania

2013

Czasopismo

Dalton Transactions

Numer woluminu

42

Strony

13404-13416

DOI

10.1039/c3dt50969a

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The behaviour of the system formed by VIVO2+ ion with all-cis-2,4,6-trimethoxycyclohexane-1,3,5-triamine (tmca) was characterized in aqueous solution through the combined application of electron paramagnetic resonance (EPR) and UV-Vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), pH-potentiometry and DFT methods. The formation of an unusual non-oxido [V(tmcaH−2)2] species with VN6 coordination, with the ligand in the bianionic form, was demonstrated. The geometry, EPR and UV-Vis spectra and electronic structure of [V(tmcaH−2)2] were simulated with Gaussian 09 and ORCA software and the results were compared with those of similar oxido and non-oxido vanadium(IV) species formed by other polyamine and polyol related ligands, such as 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci), 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci), cis-inositol (ino) and 1,3,5-trideoxy-1,3,5-trimethoxy-cis-inositol (tmci). The results indicate that VIVO2+ species are formed in acid and weakly basic solution and that [V(tmcaH−2)2] is observed above pH 10. In the non-oxido complex, DFT calculations suggest that the two –NH2 groups are in trans position and that the pre-organization of the ligands favours the metal complexation and the formation of the hexa-coordinated species with VN6 coordination.

Adres publiczny

http://dx.doi.org/10.1039/c3dt50969a

Strona internetowa wydawcy

https://www.rsc.org/

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