Nucleobase coordination chemistry

While metal-nitrogen and metal-oxygen bonded compounds dominate nucleobase coordination chemistry, examples in which metal-carbon bonds are formed have been identified. Early studies on the synthesis of metal-labeled DNA demonstrated that nucleotide-triphosphates, UTP, CTP, dUTP, and dCTP, can undergo mercury modification at C5 (82,83). The UTP derivative was also shown to act as a substrate for RNA polymerase in the presence of mercaptans (83). Later, guano-sine was shown to undergo mercury modification at C8 though, in this case, the purine was multiply substituted, 21 (84). 

Coordination compounds have become very usable in medicine [361-364]. In this respect, use of metal complexes (mostly those of lanthanides) as diagnostic [365-367] and anticancer [368-370] media should be specially emphasized. Among the last complexes, the aminoplatinum-containing compounds play an important role, so the structural study of platinum complexes as a model of nucleobases [371] is a topic of renewed interest. The new issue of Comprehensive Coordination Chemistry II [372] contains a wide description of nanoparticles (vols. 6 and 7), biocoordination chemistry (vol. 8), and other aspects of application of coordination compounds. 

N7H = 11.57 ppm). While these reactions are rather unusual with regard to metal-nucleobase chemistry, they are in fact examples of classical cyclometalation (97). Such reactions often involve a pre-coordination step, as observed in the formation of 25. 

Attempts to model the intrastrand d(GpG) crosslink with nucleobases have met with only moderate success. Usually the 06 atoms of the two guanosine rings are on opposite sides of the platinum coordination plane ( head-to-tail isomer). Only for cw-[Pt(NH3)2(9-EtG)2] was the correct isomer obtained. Nucleobase complexes of the ds-diammineplatinum(II) moiety have been valuable for testing the controversial proposal of N7,06 chelate formation, which to date has not been observed. Several interesting discoveries of metal-nucleobase chemistry are that metal binding can stabilize rare tautomers, for example, the... 

RuliSek, L., Sponer, J. (2003). Outer-shell and inner-shell coordination of phosphate group to hydrated metal ions (Mg2+, Cu>2+Zn2+> Cd2+) in the presence and absence of nucleobase. The role of nonelectrostatic effects. The Journal of Physical Chemistry B, 107,1913. 

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