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

• Authors: Jaromír Vinklarek , Jan Honzíĉek , Ivana Císařová , Martin Pavliŝta , Jana Holubová
• Languages of publication: EN

Abstracts

EN

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.

Keywords

EN

bent metallocene; 1,1-dimethylvanadocene dichloride; antitumor agent; EPR spectroscopy; X-ray diffraction analysis

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2005
• Volume: 3
• Issue: 1
• Pages: 157-168

Dates

published

1 - 3 - 2005

online

1 - 3 - 2005

Contributors

author

Jaromír Vinklarek

• The Department of General and Inorganic Chemistry, University of Pardubice, nám. Ĉs. legií 565, 532 10, Pardubice, Czech Republic

author

Jan Honzíĉek

• The Department of General and Inorganic Chemistry, University of Pardubice, nám. Ĉs. legií 565, 532 10, Pardubice, Czech Republic

author

Ivana Císařová

• Department of Inorganic Chemistry, Charles University, Hlavova 2030, 128 40, Prague 2, Czech Republic

author

Martin Pavliŝta

• Research Centre “New Inorganic Compounds and Advanced Materials”, University of Pardubice, nám. Ĉs. legií 565, 532 10, Pardubice, Czech Republic

author

Jana Holubová

• The Department of General and Inorganic Chemistry, University of Pardubice, nám. Ĉs. legií 565, 532 10, Pardubice, Czech Republic

References

• [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/cr00081a012[Crossref]
• [2] P. Köpf-Maier: “Antitumor activity of titanocene dichloride in xenografted human renal-cell carcinoma”, Anticancer Res., Vol. 19, (1999), pp. 493–504.
• [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/10.1159/000055009
• [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/10.1159/000027075[Crossref]
• [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)00236-1[Crossref]
• [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/ic9902469
• [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/om960349o[Crossref]
• [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/cccc19970265[Crossref]
• [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)81620-5[Crossref]
• [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/om030403i[Crossref]
• [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/om049679w[Crossref]
• [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.2004.04.015[Crossref]
• [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.2003.11.042[Crossref]
• [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/BF02476239[Crossref]
• [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/cccc20040811[Crossref]
• [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.
• [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. [Crossref]
• [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.
• [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.
• [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.24-2617[Crossref]
• [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.2004.07.005[Crossref]
• [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/ja00855a022[Crossref]
• [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-F[Crossref]
• [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/S0108270196002715[Crossref]
• [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/om00073a010[Crossref]
• [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)81341-8[Crossref]
• [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-X[Crossref]
• [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/S002188989400021X[Crossref]
• [29] G.M. Sheldrick: SHELXL97 Program for Crystal Structure Refinement for Diffraction Data, University of Gőttingen, Germany, 1997.

Identifiers

DOI

10.2478/BF02476246