Role of the phosphine ligands on the stabilization of monoadducts of the model nucleobases 1-methylcytosine and 9-methylguanine in platinum(II) complexes.
The addition of 1-methylcytosine (1-MeCy) or 9-methylguanine (9-MeGu) to solutions of cis-(PPh3)2P(ONO2)2 (1a), in a molar ratio of 1:1, affords the monoadducts cis-[(PPh3)2Pt(1-MeCy)(ONO2)]NO3 (2a) and cis-[(PPh3)2Pt(9-MeGu)(ONO2)]NO3 (3a) and only trace amounts of the bisadducts cis-[(PPh3)2Pt(1-MeCy)2](NO3)2 (4a) and cis-[(PPh3)2Pt(9-MeGu)2](NO3)2 (5a), respectively. The X-ray structural determination of 2a and 3a indicates a strong pi-pi stacking interaction between one of the PPh3 phenyl groups and the pyrimydinic N3-platinated cytosine or the imidazole part of the N7-coordinated guanine base. The addition of a further equiv of nucleobase to the monoadducts forms quantitatively the bisadducts that have been isolated as pure compounds 4a and 5a. Under the same experimental conditions, the dinitrato analogue cis-[(PMePh2)2Pt(ONO2)2] (1b) forms the monoadducts 2b and 3b in equilibrium with a relatively high concentration (20-30%) of the bisadducts cis-[(PMePh2)2Pt(1-MeCy)2](NO3)2 (4b) and cis-[(PMePh2)2Pt(9-MeGu)2](NO3)2 (5b), which have been structurally characterized by single-crystal X-ray analysis. The characterization of the isolated complexes by multinuclear NMR spectroscopy is also described.
Montagner
Diego
D
Dipartimento di Scienze Chimiche, Universitá di Padova, Via Marzolo 1, 35131 Padova, Italy.
Zangrando
Ennio
E
Longato
Bruno
B
D018360:Crystallography, X-Ray; D003596:Cytosine / Q000031:analogs & derivatives* / Q000737:chemistry; D006147:Guanine / Q000031:analogs & derivatives* / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D017671:Platinum Compounds / Q000737:chemistry*
D008024:Ligands; D010720:Phosphines; D017671:Platinum Compounds; C031532:1-methylcytosine; C116701:9-methylguanine; D006147:Guanine; D003596:Cytosine; C044646:phosphine