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BY-NC-ND 3.0 license Open Access Published by De Gruyter Open Access March 1, 2005

Synthesis, characterization and structure of the Bis(methyl-cyclopentadienyl)vanadium(IV) carboxylates

  • Jaromír Vinklarek EMAIL logo , Jan Honzíĉek , Ivana Císařová , Martin Pavliŝta and Jana Holubová
From the journal Open Chemistry

Abstract

The 1,1’-dimethylvanadocene dichloride ((C5H4CH3)2VCl2) reacts in aqueous solution with various carboxylic acids giving two different types of complexes. The 1,1’-dimethylvanadocene complexes of monocarboxylic acids (C5H4CH3)2V(OOCR)2 (R=H,CCl3, CF3, C6H5) contain two monodentate carboxylic ligands, whereas oxalic and malonic acids act as chelate compounds of the formula (C5H4CH3)2V(OOC-A-COO) (A=−, CH2). The structure of the (C5H4CH3)2 V(OOCCF3)2 complex was determined by single crystal X-ray diffraction analysis. The isotropic and anisotropic EPR spectra of all the complexes prepared were recorded. The obtained EPR parameter values were found to be in agreement with proposed structures.

[1] P. Köpf-Maier and H. Köpf: “Non-Platinum-Group Metal Antitumor Agents: History, Current Status, and Perspectives”, Chem. Rev., Vol. 87, (1987), pp. 1137–1152. http://dx.doi.org/10.1021/cr00081a01210.1021/cr00081a012Search in Google Scholar

[2] P. Köpf-Maier: “Antitumor activity of titanocene dichloride in xenografted human renal-cell carcinoma”, Anticancer Res., Vol. 19, (1999), pp. 493–504. Search in Google Scholar

[3] K. Mross, P. Robben-Bathe, L. Edler, J. Baumgart, W. E. Berdel, H. Fiebig and C. Unger: “Phase I clinical trial of a day −1, −3, −5 every 3 weeks schedule with titanocene dichloride (MKT 5) in patients with advanced cancer: A study of the phase I study group of the Association for Medical Oncology (AIO) of the German Cancer Society”, Onkologie, Vol. 23, (2000), pp. 576–579. http://dx.doi.org/10.1159/00005500910.1159/000055009Search in Google Scholar

[4] N. Kroger, U.R. Kleeberg, K. Mross, L. Edler, G. Sass and D.K. Hossfeld: “Phase II clinical trial of titanocene dichloride in patients with metastatic breast cancer”, Onkologie, Vol. 23, (2000), pp. 60–62. http://dx.doi.org/10.1159/00002707510.1159/000027075Search in Google Scholar

[5] P. Ghosh, S. Ghosh, C. Navara, R.K. Narla, A. Benyumov and F.M. Uckun: “X-ray structure, solution properties, and biological activity profile of vanadocene(IV) acetylacetonate complex, [VCp2(acac)](CF3SO3): A dual-function anti-cancer agent with anti-angiogenic and anti-mitotic properties”, J. Inorg. Biochem., Vol. 84, (2001). pp. 241–253. http://dx.doi.org/10.1016/S0162-0134(00)00236-110.1016/S0162-0134(00)00236-1Search in Google Scholar

[6] P. Ghosh, A.T. Kotchevar, D.D. DuMez, S. Ghosh, J. Peiterson and F.M. Uckun: “Synthesis and structure of bis(π-cyclopentadeenyl)vanadium(IV) 1,10-phenanthroline and 2,2′-bipyridine compounds and their interactions with artificial membranes”, Inorg. Chem., Vol. 38, (1999), pp. 3730–3737. http://dx.doi.org/10.1021/ic990246910.1021/ic9902469Search in Google Scholar

[7] J.A. Belot, R.D. McCullough, A.L. Rheingold and G.P.A. Yap: “A facile and efficient method for preparing ring-alkylated vanadocenes (RCp)2V and mono- and dichlorides of ring- alkylated vanadocenes (RCp)2VCl and (RCp)2VCl2”, Organometallics, Vol. 15, (1996), pp. 5062–5065. http://dx.doi.org/10.1021/om960349o10.1021/om960349oSearch in Google Scholar

[8] B. Dorer, M.H. Prosenc, U. Rief and H.H. Brintzinger: “Ansa-vanadocene complexes —Syntheses, structures and ligand exchange reactions”, Collect. Czech. Chem. Commun., Vol. 62, (1997), pp. 265–278. http://dx.doi.org/10.1135/cccc1997026510.1135/cccc19970265Search in Google Scholar

[9] P. Köpf-Maier, S. Grabowski, J. Liegener and H. Köpf: “New Antitumor Titanocene Derivatives Containing Hydrophilic Ligands”, Inorg. Chim. Acta-Bioinorg. Chem. Vol. 108, (1985), pp. 99–103. http://dx.doi.org/10.1016/S0020-1693(00)81620-510.1016/S0020-1693(00)81620-5Search in Google Scholar

[10] O.R. Allen, L. Croll, A.L. Gott, R.J. Knox and P.C. McGowan: “Functionalized cyclopentadienyl titanium organometallic compounds as new antitumor drugs”, Organometallics, Vol. 23, (2004), pp. 288–292. http://dx.doi.org/10.1021/om030403i10.1021/om030403iSearch in Google Scholar

[11] P.W. Causey, M.C. Baird and S.P.C. Cole: “Synthesis, Characterization, and Assessment of Cytotoxic Properties of a Series of Titanocene Dichloride Derivatives”, Organometallics, Vol. 23, (2004), pp. 4486–4494. http://dx.doi.org/10.1021/om049679w10.1021/om049679wSearch in Google Scholar

[12] M. Tacke, L.T. Allen, L. Cuffe, W.M. Gallagher, Y. Lou, O. Mendoza, H. Müller-Bunz, F.-J.K. Rehmann and N. Sweeney: “Novel titanocene anti-cancer drugs derived from fulvenes and titanium dichloride”, J. Organoment. Chem., Vol. 689, (2004), pp. 2242–2249. http://dx.doi.org/10.1016/j.jorganchem.2004.04.01510.1016/j.jorganchem.2004.04.015Search in Google Scholar

[13] J. Honzíček, P. Nachtigall, I. Císařova and J. Vinklárek: “Synthesis, characterization and structural investigation of the first vanadocene(IV) carboxylic acid complexes prepared from the vanadocene dichloride”, J. Organomet. Chem. Vol. 689, (2004), pp. 1180–1187. http://dx.doi.org/10.1016/j.jorganchem.2003.11.04210.1016/j.jorganchem.2003.11.042Search in Google Scholar

[14] J. Vinklárek, J. Honzíček and Jana Holubová: “Inclusion compounds of cystostatic active (C5H5)2VCl2 and (CH3C5H4)2VCl2 with α−, β− and γ− cyclodextrines: Synthesis, EPR study and microbiological behavior toward Escherichia coli”, Central European Journal of Chemistry, Vol. 3, (2005), pp. 72–81. http://dx.doi.org/10.2478/BF0247623910.2478/BF02476239Search in Google Scholar

[15] J. Vinklárek, H. Paláčková and J. Honzíček: “Experimental and theoretical study of the first vanadocene(IV) complexes of α-amino acids prepared from vanadocene dichloride”, Collect. Czech. Chem. Commun., Vol. 69, (2004), pp. 811–821. http://dx.doi.org/10.1135/cccc2004081110.1135/cccc20040811Search in Google Scholar

[16] I. Pavlík and J. Vinklárek: “Hydrolysis Behavior of the Antitumor Agent Vanadocene Dichloride in Strongly Acid, Neutral and Alkaline Aqueous-Media-an EPR Study”, Eur. J. Solid State Inorg. Chem., Vol. 28, (1991), pp. 815–827. Search in Google Scholar

[17] L. Phillips, A.R. Lacey and M.K. Cooper: “Analysis of Substituted Ferrocenes by Infrared-Spectroscopy”, J. Chem. Soc.-Dalton Trans., Vol., (1988), pp. 1383–1391. Search in Google Scholar

[18] K. Nakamoto: “Complexes of Carboxylic Acids”, In: K. Nakamoto: Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, 5th Ed., Wiley, New York, 1997, pp. 59–62. Search in Google Scholar

[19] K. Nakamoto: “Complexes of Oxalato and Related Ligands”, In: K. Nakamoto: Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, 5th Ed., Wiley, New York, 1997, pp. 74–79. Search in Google Scholar

[20] Z. Náhlovská, B. Náhlovský and T.G. Strand: “Molecular Structure of Gaseous Oxalic Acid from Electron Diffraction and IR data”, Acta Chem. Scand., Vol. 24, (1970), p. 2617–2628. http://dx.doi.org/10.3891/acta.chem.scand.24-261710.3891/acta.chem.scand.24-2617Search in Google Scholar

[21] J. Honzíček, J. Vinklárek and P. Nachtigall: “A density functional study of EPR hyperfine coupling for vanadocene(IV) complexes”, Chem. Phys., Vol. 305, (2004), pp. 291–298. http://dx.doi.org/10.1016/j.chemphys.2004.07.00510.1016/j.chemphys.2004.07.005Search in Google Scholar

[22] J. Petersen and F. Dahl: “Synthesis and Structural Characterization by X-Ray Diffraction and Elactron Paramagnetic Resonance Single-Crystal Techniques of V(η 5-C5H4CH3)2Cl2 and Ti(η 5-C5H4CH3)2Cl2. A Study of the Spatial Distribution of the Unpaired Electron in a V(η 5-C5H5)2L2-Type Complex”, J. Am. Chem. Soc., Vol. 97, (1975), pp. 6422–6433. http://dx.doi.org/10.1021/ja00855a02210.1021/ja00855a022Search in Google Scholar

[23] G.S. Herrmann, H.G. Alt and U. Thewalt: “Titanocene Trifluoroacetato Complexes: The Molecular Structure of [Cp2Ti(OCOCF3)]2μ−O and Cp2Ti(OCOCF3)2”, J. Organomet. Chem., Vol. 399, (1990), pp. 83–92. http://dx.doi.org/10.1016/0022-328X(90)80086-F10.1016/0022-328X(90)80086-FSearch in Google Scholar

[24] D.H. Gibson, Y. Ding, J.F. Richardson and M.S. Mashuta: “Bis(η 5-cyclopentadienyl)bis(formato-O)titanium”, Acta Crystallogr. Sect. C-Cryst. Struct. Commun., Vol. 52, (1996), pp. 1614–1616. http://dx.doi.org/10.1107/S010827019600271510.1107/S0108270196002715Search in Google Scholar

[25] D.M. Hoffman, N.D. Chester and R.C. Fay: “Bent Metallocenes Containing Potentially Bidentate Ligands. The Crystal and Molecular Structure of Bis(ν-cyclopentadienyl)bis(benzoato)titanium(IV)”, Organometallics, Vol. 2, (1983), pp. 48–52. http://dx.doi.org/10.1021/om00073a01010.1021/om00073a010Search in Google Scholar

[26] Y.K. Zhou, Z.Q. Wang, X. Wang and Y. Zhu: “Synthesis, Characterization and Structure of Carboxylate Derivatives of Bis(methylcyclopentadienyl)titanium(IV)”, Polyhedron, Vol. 9, (1990), pp. 783–787. http://dx.doi.org/10.1016/S0277-5387(00)81341-810.1016/S0277-5387(00)81341-8Search in Google Scholar

[27] Z. Otwinowski and W. Minor: “Processing of X-ray diffraction data collected in oscillation mode”, In: Methods Enzymol. Part A: Macromolecular Crystallography, Vol. 276, Academic Press, San Diego, 1997, pp. 307–326. http://dx.doi.org/10.1016/S0076-6879(97)76066-X10.1016/S0076-6879(97)76066-XSearch in Google Scholar

[28] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M.C. Burla, G. Polidori, and M. Camalli: “SIRPOW. 92-a program for automatic solution of crystal structures by direct methods optimized for powder data”, J. Appl. Cryst., Vol. 27, (1994), pp. 435–436. http://dx.doi.org/10.1107/S002188989400021X10.1107/S002188989400021XSearch in Google Scholar

[29] G.M. Sheldrick: SHELXL97 Program for Crystal Structure Refinement for Diffraction Data, University of Gőttingen, Germany, 1997. Search in Google Scholar

Published Online: 2005-3-1
Published in Print: 2005-3-1

© 2005 Versita Warsaw

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