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EuAsC 2 S-12/S 1 -OP1 A New Twist in Aqueous Cisplatin Chemistry: Intermolecular Condensation Reactions Between Pt-OH and Pt-NH 3 Ligands B.Lippert , a L.Yin, a S.Siebel, a G.Kampf, a P.Brandi Blanco, a W.-Z.Shen, a P.J.Sanz Miguel a,b a Faculty of Chemistry, TU Dortmund, 44221 Dortmund, Germany b Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, 50009 Zaragoza, ([email protected]) Reactions between hydrolysis products of Cisplatin (cis-PtCl 2 (NH 3 ) 2 ) with nucleobases can formally be divided into substitution reactions of Pt-OH 2 ligands by neutral N-donors, or by condensation reactions between Pt-OH groups and weakly acidic N-H entities of nucleobases. Guanine-N7 coordination of Pt II is an example of the first type, while Thymine-N3 platination is an example of the second one. For kinetic reasons the first option is generally favored, but the second one is likewise established both for DNA and model nucleobase systems. As far as the chemistry of Cisplatin in water is concerned, self-condensation reactions of hydrolysis species, hence between Pt-OH 2 and Pt-OH groups to give hydroxo-bridged species, are well established since the 1970s. In contrast, relatively little is known about possible condensation reactions involving am(m)ine ligands of Pt II and Pt-OH groups to give amido-bridged compounds in water. Originally observed by us in heteronuclear Pt,Pd complexes derived from trans-(NH 3 ) 2 Pt II and pyrazole [1], amide bridge formation has later also been established for complexes derived from trans- (CH 3 NH 2 ) 2 Pt II [2] and eventually also for Pt,Pd and Pt,Pd,Ag complexes obtained from cis- (NH 3 ) 2 Pt II and the model nucleobase 1-methylcytosine [3, 4]. We now have conclusive evidence that NH 2 - bridging is also possible in homonuclear Pt n complexes isolated from water [5]. Interestingly, amide bridging in these multinuclear complexes occurs concomitantly with hydroxo and nucleobase bridge formation. Spectroscopic and X-ray crystallographic data will be presented to provide evidence for this new aspect of Cisplatin chemistry in water. Acknowledgments: Financial support from DFG, TU Dortmund, IMPRS (W.-Z.S.), Ramón Areces Foundation (P.B.B.), and the Ramón y Cajal programme (P.J.S.M.) are gratefully acknowledged. References [1] A. Schneider, E. Freisinger, B. Beck, B. Lippert, J.Chem.Soc.,Dalton Trans. 2000, 837. [2] P. Brandi Blanco, P. J. Sanz Miguel, B. Lippert, Dalton Trans. 2011, 40, 10316. [3] L. Yin, P. J. Sanz Miguel, W.-Z. Shen, B. Lippert, Chemistry - Eur. J. 2009, 15, 10723. [4] G. Kampf, P. J. Sanz Miguel, M. Morell Cerdà, M. Willermann, A. Schneider, B. Lippert, Chemistry – Eur. J. 2008, 14, 6882. [5] L. Yin, P. J. Sanz Miguel, B. Lippert, to be published.
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