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Additional resources for Progress in Inorganic Chemistry, Volume 37

Example text

Formation of a C-N3,A-N7intrastrand cross-link in DNA and, similarly, the corresponding T,A cross-link would require virtually the same conformational changes as the G,C cross-link (cf. 4), namely. an anti +. syn rotation of one of the two bases about the glycosidic bond. 5) were quite informative because a distinct difference in donor site preference for the A ligand could be seen (235). While the cis isomer preferred the N7 site over N1 by a factor of 17, the trans isomer preferred N1 slightly over N7 (4:3) under comparable conditions.

Molecular cations of c1s- and tran~-((NH,)~Pt(l-MeC)(9-MeA)J~ Reprinted with permission from [R Beyerle-Pfnur, B Brown, R Faggiani. B Lippert, and C J L Lock, Inorg Chem , 24, 4001 (1985)l Copyright (1985) American Chemical Society 50 PLATINUM NUCLEORASE CHEMISI'RY 51 5. I>@erentiation of Binding Sites by IK arid Raman Spectroscopy A differentiation of adenine N1 and N7 platinum binding usually requires pHdependent spectroscopic studies (UV, NMR) or X-ray analysis. Within the 9-MeA/Pt(II) system, however, marker bands in the IR and Raman spectra have been established that permit rapid assignment of the Pt coordination site(s).

In this dinuclear complex, the two metals [Pt. 981(2) A] are bound through N3 and the deprotonated exocyclic N4, with the two ligands arranged head-tail. 4 Hz). The significance of Pt binding to N4 comes from the fact that displacement of the extremely weakly acidic amino proton [pKa 2 14 (254)] at N4 by Pt(I1) takes place in neutral and even moderately acidic solution. It is believed that coordination at N4 occurs in a pH-independent condensation reaction between a Pt-OH moiety and the H-N(4) entity, leading to a thermodynamically very stable product.

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