Exploring water-soluble Pt(II) complexes of diethylenetriamine derivatives functionalized at the central nitrogen. Synthesis, characterization, and reaction with 5′-GMP

The aims of our program are to develop coordination complexes that can be used as selective probes, fluorescent agents and inorganic medicinal agents. In order to accomplish this, the design, synthesis, characterization and X-ray structure of new water-soluble monofunctional Pt(II) complexes with useful spectroscopic properties for assessing metal binding to biomolecules were investigated. Two diethylenetriamine (dien) derivatives, 2-(bis(2-aminoethyl)amino)acetic acid (acdien) and N′-[7-(acetamido)-4-(trifluoromethyl)coumarin]diethylenetriamine (atfcdien), were used. The latter was designed to allow the fluorophore group, 7-amino-4-(trifluoromethyl)coumarin (atfc), to be attached to metal centers through the dien moiety. 1H NMR spectroscopy and X-ray crystallography were employed to characterize the [Pt(atfcdien)Br][Pt(Me2SO)Br3] (8a) and [Pt(acdien)Br]Br (9a) complexes. 1H NMR and fluorescence spectroscopic methods were used to characterize the [Pt(atfcdien)Br]Br (8b) and [Pt(acdien)Br]Br (9a) complexes. 1H NMR studies of the monofunctional [Pt(acdien)Br]Br (9a) complex conducted to examine its interaction with guanosine 5′-monophosphate (5′-GMP) in D2O solutions revealed one downfield-shifted H8 and one downfield-shifted H1′ signal, consistent with 5′-GMP binding via N7 and fast rotation about the Pt–N7 bond.

New platinum(II) complexes of the new N′-[7-(acetamido)-4-(trifluoromethyl)coumarin]diethylenetriamine (atfcdien) ligand and of the 2-(bis(2-aminoethyl)amino)acetic acid (acdien) ligand were structurally characterized, including an unusual [Pt(atfcdien)Br][Pt(dimethylsulfoxide)Br3] salt. The Pt partially quenches coumarin fluorescence. The Pt(acdien)(guanosine 5′-monophosphate) adduct exhibits fast rotation about the Pt–N7 bond to the guanine nucleobase in D2O solution.Figure optionsDownload as PowerPoint slide