ABSTRACT
The primary amine MeNH(2), when bonded to Pt(II), is converted into a methylamide bridge upon coordination of a second, different metal ion (Pd(II)), thereby making the N atom chiral.
ABSTRACT
Metal nucleobase complexes provide a potential for acid-base chemistry in the physiological pH range and consequently may contribute or be actively involved in catalytic reactions of nucleic acids, notably of RNAs. Expansion of the available pH range is achieved if additional ligands are involved, for example, an aqua ligand or a second nucleobase, and if relevant pK(a) values are sufficiently close. Two bpy's (bpy = 2,2'-bipyridine) containing Pt(II) complexes have been studied in this context: [Pt(bpy)(9-MeGH-N7)(2)](NO(3))(2) x H(2)O (2) and Pt(bpy)(9-EtG-N7)(9-EtG-N1) x 3 H(2)O (3') (with 9-MeGH = 9-methylguanine; 9-EtGH = 9-ethylguanine). Relevant pK(a) values, as determined by pD-dependent (1)H NMR spectroscopy in D(2)O, of the neutral guanine ligands were found to be ca. 7.78 +/- 0.01 and 8.38 +/- 0.01 for 2, yet 4.00 +/- 0.03 and 7.7 +/- 0.1 for 3' (values converted to H(2)O) for each of the two guanine ligands. These values suggest that complex 3' provides a pH range of roughly 4-8 for potential acid-base chemistry, and furthermore that in favorable cases compounds with two ionizable ligands can function as an acid and a base simultaneously. X-ray crystal structures of both 2 and 3' are presented and, in addition, that of [Pt(bpy)(9-EtGH-N7)(2)](NO(3))(2) x (9-EtGH) x 5 H(2)O (2''). Regarding the use of (1)H NMR spectroscopy for the determination of pK(a) values, we note that chemical shifts referenced to sodium 3-(trimethylsilyl)propanesulfonate must be treated with caution when applying cationic complexes because of the possibility of ion pairing. It can lead to mistakes in chemical shift values.