Complex Formation of Vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands (Articolo in rivista)

Type
Label
  • Complex Formation of Vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands (Articolo in rivista) (literal)
Anno
  • 2004-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ic0352046 (literal)
Alternative label
  • Morgenstern B., Steinhauser S., Hegetschweiler K., Garribba E., Micera G., Sanna D., Nagy L. (2004)
    Complex Formation of Vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands
    in Inorganic chemistry
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Morgenstern B., Steinhauser S., Hegetschweiler K., Garribba E., Micera G., Sanna D., Nagy L. (literal)
Pagina inizio
  • 3116 (literal)
Pagina fine
  • 3126 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://pubs.acs.org/doi/abs/10.1021/ic0352046 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 43 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Anorganische Chemie, Universität des Saarlandes, Postfach 15 11 50, D-66041 Saarbrücken, Germany Dipartimento di Chimica, Università degli Studi di Sassari, Via Vienna 2, I-07100 Sassari, Italy Istituto di Chimica Biomolecolare, CNR, Traversa La Crucca 3, I-07040 Li Punti, Sassari, Italy Department of Inorganic and Analytical Chemistry, University of Szeged, P.O. Box 440, 6701 Szeged, Hungary (literal)
Titolo
  • Complex Formation of Vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands (literal)
Abstract
  • The complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci) was studied in aqueous solution and in the solid state. The formation constants of [VIVO(taci)]2+, [VIVO(tdci)]2+, and [VIV(tdci)2]4+ and of the deprotonation product [VIV(tdci)2H-1]3+ were determined (25 °C, 0.1 M KNO3). Cyclic voltammetry measurements established a reversible one-electron transfer for the [VIV(tdci)2H-m](4-m)/[VIII(tdci)2H-n](3-n) couple (0 <= n, m <= 6) with a strongly pH-dependent E1/2obs (+0.15 V at pH 5, -0.57 V at pH 13.5). Slightly more negative potentials were measured for the taci complexes. An additional quasi-reversible electron transfer at strongly positive potentials (1.2-0.5 V) was assigned to the [VV(taci)2H-m](5-m)/[VIV(taci)2H-n](4-n) couple. The structures of [VIV(taci)2](SO4)2·12H2O (1), [VIV(tdci)2][V4VO12]·14.5H2O (2), and [VIV(tdci)2H-1]Cl3·15H2O (3) were determined by single-crystal X-ray analysis. The cations of 1-3 exhibit a structure of approximate D3d symmetry. The vanadium centers have an almost regular octahedral geometry. The coordinated oxygen donors are deprotonated, and their protons are transferred to the amino groups which act as internal bases. For both ligands, EPR measurements support the formation of non-oxo VIV complexes, with a dz2 ground state, in aqueous solution above pH 7. The spectral features are indicative of hexacoordinated complexes with a geometry distorted toward a trigonal prism. Finally, a mechanism is proposed for the decomposition of [VIVL2H-x](4-x) (L = taci and tdci) in strongly alkaline media (pH ? 13). (literal)
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