Abstract
Dichloro(ethylenediamine)platinum(II), Pt(en)Cl2, was dissolved in H2O and D2O, and the resulting aqueous solutions were electrosprayed into a quadrupole ion-trap mass spectrometer. A series of major and minor ionic hydrolysis products were detected. These ions were then subjected to collision-induced dissociation. As an aid in interpreting the experimental results, density functional theory calculations were carried out. These computations permitted the structures and energetics associated with the hydrolysis products to be determined. An understanding of the hydrolysis of PtenCl2 and related coordination complexes is essential in the rational design of metal-based drugs.
Article PDF
Similar content being viewed by others
References
Rosenberg, B.; Van Camp, L.; Trosko, J. R.; Mansour, V. A. Platinum Compounds: A New Class of Potent Antitumor Agents. Nature 1969, 222, 385.
Sherman, S. E.; Lippard, S. J. Structural Aspects of Platinum Anticancer Drug Interactions with DNA. Chem. Rev. 1987, 87, 1153–1181.
Platinum-Based Drugs in Cancer Therapy; Kendall, L. R.; Farrell, N. P., Eds. Humana Press: Totowa, NJ, 2000.
Fuertes, M. A.; Alonso, C.; Perez, J. M. Biochemical Modulation of Cisplatin Mechanisms of Action: Enhancement of Antitumor Activity and Circumvention of Drug Resistance. Chem. Rev. 2003, 103, 645–662.
Kasparkova, J.; Zehnulova, J.; Farrell, N.; Brabec, V. DNA Interstrand Cross-links of the Novel Antitumor Trinuclear Platinum Complex BBR3464: Conformation, Recognition by High Mobility Group Domain Proteins, and Nucleotide Excision Repair. J. Biol. Chem. 2002, 277, 48076–48086.
Wyatt, K. S.; Harrison, K. N.; Jensen, C. M. Release of Platinum from Cysteine Residues Induced by N,S-Donor Chelation. Inorg. Chem. 1992, 31, 3867–3868.
Martin, R. B. Platinum Complexes: Hydrolysis and Binding to N(7) and N(1) of Purines; Wiley VCH: New York, 1999.
Djuran, M. I.; Lempers, E. L. M.; Reedijk, J. Reactivity of Chloro- and Aqua(Diethylenetriamine) Platinum(II) Ions with Glutathione, S-Methylglutathione, and Guanosine 5′-Monophosphate in Relation to the Antitumor Activity and Toxicity of Platinum Complexes. Inorg. Chem. 1991, 30, 2648–2652.
Bach, S. B. H.; Sepeda, T. G.; Merrill, G. N.; Walmsley, J. A.. J. Am. Soc. Mass Spectrom. 2005, 16, 1461–1469.
Bach, S. B. H.; Green, C. E.; Nagore, L. I.; Sepeda, T. G.; Merrill, G. N. Complexes of Dichloro(Ethylenediamine)Palladium(II) Observed from Aqueous Solutions by Electrospray Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2007, 18, 769–777.
Rochon, F. D.; Buculei, V. Multinuclear Magnetic Resonance Spectroscopy and Crystal Structures of Iodo-bridged Dinuclear Pt(II) Complexes with Amines. Inorg. Chim. Acta 2005, 358, 3919–3926.
Henderson, W.; Sabat, M. Platinum(II)- and Palladium(II)-Amide Complexes [M{NC(O)CH2CH2CH2}2L2] Derived from 2-Azetidinone (b-Propiolactam); a Synthetic, Electrospray Mass Spectrometric and X-Ray Crystallographic Study. Polyhedron 1997, 16, 1663–1677.
Vrkic, A. K.; O’Hair, R. A. J. Gas Phase Ion Chemistry of Para-Substituted Benzene Diazonium Ions, Their Salt Clusters and Their Related Phenyl Cations. Int. J. Mass Spectrom. 2002, 218, 131–160.
Shukla, A. K.; Futrell, J. H. Tandem Mass Spectrometry: Dissociation of Ions by Collisional Activation. J. Mass Spectrom. 2000, 35, 1069–1090.
Becke, A. D. Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior. Phys. Rev. 1988, A38, 3098–3100.
Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. 1988, B37, 785–789.
Becke, A. D. A New Mixing of Hartree-Fock and Local-Density-Functional Theories. J. Chem. Phys. 1993, 98, 1372–1377.
Stevens, W. J.; Basch, H.; Krauss, M. J. Compact Effective Potentials and Efficient Shared-Exponent Basis Sets for the First- and Second-Row Atoms. J. Chem. Phys. 1984, 81, 6026–6033.
Stevens, W. J.; Krauss, M. J.; Basch, H.; Jasien, P. G. Relativistic Compact Effective Potentials and Efficient, Shared-Exponent Basis Sets for the Third-, Fourth-, and Fifth-Row Atoms. Canad. J. Chem. 1992, 70, 612–630.
Cundari, T. R.; Stevens, W. J. Effective Core Potential Methods for the Lanthanides. J. Chem. Phys. 1993, 98, 5555–5565.
Hariharan, P. C.; Pople, J. A. The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies. Theor. Chim. Acta. 1973, 28, 213–222.
Pierotti, R. A. A Scaled Particle Theory of Aqueous and Nonaqueous Solutions. Chem. Rev. 1976, 76, 717–726.
Langlet, J.; Claverie, P.; Caillet, J.; Pullman, A. Improvements of the Continuum Model. 1: Applications to the Calculation of the Vaporization Thermodynamic Quantities of Nonassociated Liquids. J. Phys. Chem. 1988, 92, 1617–1631.
Amovilli, C.; Mennucci, B. Self-Consistent Field Calculation of Pauli Repulsion and Dispersion Contributions to the Solvation Free Energy in the Polarizable Continuum Model. J. Phys. Chem. B 1997, 101, 1051–1057.
Mennucci, B.; Tomasi, J. Continuum Solvation Models: A New Approach to the Problem of Solute’s Charge Distribution and Cavity Boundaries. J. Chem. Phys. 1997, 106, 5151–5158.
Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S.; Windus, T. L.; Montgomery, J.; Dupuis, M. General Atomic and Molecular Electronic Structure System. J. Comput. Chem. 1993, 14, 1347–1363.
Coley, R. F.; Martin, D. S. Kinetics and Equilibria for the Acid Hydrolysis of Dichloro(Ethylenediamine)Platinum(II). Inorg. Chim. Acta. 1973, 7, 573–577.
Costa, L. A. S.; Rocha, W. R.; De Almeida, W. B.; Dos Santos, H. F. The Hydrolysis Process of the cis-Dichloro(Ethylenediamine)Platinum(II): A Theoretical Study. J. Chem. Phys. 2003, 118, 10584–10592.
Costa, L. A. S.; Rocha, W. R.; De Almeida, W. B.; Dos Santos, H. F. The Solvent Effect on the Aquation Processes of the cis-Dichloro(Ethylenediamine)Platinum(II) Using Continuum Solvation Models. Chem. Phys. Lett. 2004, 387, 182–187.
Møller, C.; Plesset, M. S. Note on the Approximation Treatment for Many-Electron Systems. Phys. Rev. 1934, 46, 618–622.
Binkley, J. S.; Pople, J. A. Møller-Plesset Theory for Atomic State Energies. Int. J. Quantum Chem. 1975, 9, 229–236.
Henderson, W.; Nicholson, B. K.; McCaffrey, L. J. Applications of Electrospray Mass Spectrometry in Organometallic Chemistry. Polyhedron 1998, 17, 4291–4313.
Somorjai, G. A.; Rupprechter, G. The Flexible Surface: Molecular Studies Explain the Extraordinary Diversity of Surface Chemical Properties. J. Chem. Edu. 1998, 75, 162–176.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online December 9, 2008
Rights and permissions
About this article
Cite this article
Yoshikawa, A., Bach, S.B.H. & Merrill, G.N. An experimental and theoretical investigation into the hydrolysis of dichloro(ethylenediamine)platinum(II) via electrospray mass spectrometry and density functional theory. J Am Soc Mass Spectrom 20, 1015–1029 (2009). https://doi.org/10.1016/j.jasms.2008.11.027
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2008.11.027