A new dinuclear Ti(IV)-peroxo-citrate complex from aqueous solutions. Synthetic, structural, and spectroscopic studies in relevance to aqueous titanium(IV)-peroxo-citrate speciation

M. Dakanali, E. T. Kefalas, C. P. Raptopoulou, A. Terzis, G. Voyiatzis, I. Kyrikou, T. Mavromoustakos, A. Salifoglou

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Abstract

The wide use of titanium in applied materials has prompted pertinent studies targeting the requisite chemistry of that metal's biological interactions. In order to understand such interactions as well as the requisite titanium aqueous speciation, we launched investigations on the synthesis and spectroscopic and structural characterization of Ti(IV) species with the physiological citric acid. Aqueous reactions of TiCl4 with citric acid in the presence of H2O2 and neutralizing ammonia afforded expediently the red crystalline material (NH4)4[Ti2(O 2)2(C6H 4O7)2]·2H2O (1). Complex 1 was further characterized by UV-vis, FT-IR, FT- and laser-Raman, NMR, and finally by X-ray crystallography. Compound 1 crystallizes in the monoclinic space group P21/n, with a = 10.360(4) Å, b = 10.226(4) Å, c = 11.478(6) Å, β = 107.99(2)°, V = 1156.6(9) Å3, and Z = 2. The X-ray structure of 1 reveals a dinuclear anionic complex containing a TiIV 2O2 core. In that central unit, two fully deprotonated citrate ligands are coordinated to the metal ions through their carboxylate moieties in a monodentate fashion. The central alkoxides serve as bridges to the two titanium ions. Also attached to the TiIV 2O2 core are two peroxo ligands each bound in a side-on fashion to the respective metal ions. NH4 + ions neutralize the 4- charge of the anion in 1, further contributing to the stability of the derived lattice through H-bond formation. The structural similarities and differences with congener vanadium-(V)-peroxo-citrate complexes may point out potential implications in the chemistry of titanium with physiological ligands, when the former is present in a biologically relevant medium.

Original languageEnglish (US)
Pages (from-to)4632-4639
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number15
StatePublished - Jul 28 2003

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citrates
Titanium
Citric Acid
titanium
aqueous solutions
citric acid
Ligands
ligands
Metal ions
metal ions
Ions
chemistry
congeners
Vanadium
Raman lasers
X ray crystallography
alkoxides
Ammonia
vanadium
carboxylates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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A new dinuclear Ti(IV)-peroxo-citrate complex from aqueous solutions. Synthetic, structural, and spectroscopic studies in relevance to aqueous titanium(IV)-peroxo-citrate speciation. / Dakanali, M.; Kefalas, E. T.; Raptopoulou, C. P.; Terzis, A.; Voyiatzis, G.; Kyrikou, I.; Mavromoustakos, T.; Salifoglou, A.

In: Inorganic Chemistry, Vol. 42, No. 15, 28.07.2003, p. 4632-4639.

Research output: Contribution to journalArticle

Dakanali, M, Kefalas, ET, Raptopoulou, CP, Terzis, A, Voyiatzis, G, Kyrikou, I, Mavromoustakos, T & Salifoglou, A 2003, 'A new dinuclear Ti(IV)-peroxo-citrate complex from aqueous solutions. Synthetic, structural, and spectroscopic studies in relevance to aqueous titanium(IV)-peroxo-citrate speciation', Inorganic Chemistry, vol. 42, no. 15, pp. 4632-4639.
Dakanali, M. ; Kefalas, E. T. ; Raptopoulou, C. P. ; Terzis, A. ; Voyiatzis, G. ; Kyrikou, I. ; Mavromoustakos, T. ; Salifoglou, A. / A new dinuclear Ti(IV)-peroxo-citrate complex from aqueous solutions. Synthetic, structural, and spectroscopic studies in relevance to aqueous titanium(IV)-peroxo-citrate speciation. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 15. pp. 4632-4639.
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abstract = "The wide use of titanium in applied materials has prompted pertinent studies targeting the requisite chemistry of that metal's biological interactions. In order to understand such interactions as well as the requisite titanium aqueous speciation, we launched investigations on the synthesis and spectroscopic and structural characterization of Ti(IV) species with the physiological citric acid. Aqueous reactions of TiCl4 with citric acid in the presence of H2O2 and neutralizing ammonia afforded expediently the red crystalline material (NH4)4[Ti2(O 2)2(C6H 4O7)2]·2H2O (1). Complex 1 was further characterized by UV-vis, FT-IR, FT- and laser-Raman, NMR, and finally by X-ray crystallography. Compound 1 crystallizes in the monoclinic space group P21/n, with a = 10.360(4) {\AA}, b = 10.226(4) {\AA}, c = 11.478(6) {\AA}, β = 107.99(2)°, V = 1156.6(9) {\AA}3, and Z = 2. The X-ray structure of 1 reveals a dinuclear anionic complex containing a TiIV 2O2 core. In that central unit, two fully deprotonated citrate ligands are coordinated to the metal ions through their carboxylate moieties in a monodentate fashion. The central alkoxides serve as bridges to the two titanium ions. Also attached to the TiIV 2O2 core are two peroxo ligands each bound in a side-on fashion to the respective metal ions. NH4 + ions neutralize the 4- charge of the anion in 1, further contributing to the stability of the derived lattice through H-bond formation. The structural similarities and differences with congener vanadium-(V)-peroxo-citrate complexes may point out potential implications in the chemistry of titanium with physiological ligands, when the former is present in a biologically relevant medium.",
author = "M. Dakanali and Kefalas, {E. T.} and Raptopoulou, {C. P.} and A. Terzis and G. Voyiatzis and I. Kyrikou and T. Mavromoustakos and A. Salifoglou",
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AU - Dakanali, M.

AU - Kefalas, E. T.

AU - Raptopoulou, C. P.

AU - Terzis, A.

AU - Voyiatzis, G.

AU - Kyrikou, I.

AU - Mavromoustakos, T.

AU - Salifoglou, A.

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