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

Łodyga-Chruścińska, Elzbieta and Szebesczyk, Agnieszka and Sanna, Daniele and Hegetschweiler, Kaspar and Micera, Giovanni and Garribba, Eugenio (2013) Formation in aqueous solution of a non-oxido VIV complex with VN6 coordination: potentiometric, ESI-MS, spectroscopic and computational characterization. Dalton Transactions, Vol. 42 (37), p. 13404-13416. eISSN 1477-9234. Article.

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DOI: 10.1039/c3dt50969a

Abstract

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.

Item Type:Article
ID Code:9211
Status:Published
Refereed:Yes
Uncontrolled Keywords:Non-oxido VIV complex, electron paramagnetic resonance (EPR), aqueous solution
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01-a Nuovi Dipartimenti dal 2012 > Chimica e Farmacia
002 Altri enti e centri di ricerca del Nord Sardegna > CNR-Consiglio Nazionale delle Ricerche > Istituto di chimica biomolecolare, Sassari
Publisher:Royal Society of Chemistry
eISSN:1477-9234
Deposited On:27 Sep 2013 13:22

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