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Minor groove site coordination of adenine by platinum group metal ions: Effects on basicity, base pairing, and electronic structure

Lookup NU author(s): David Amantia, Clayton Price, Michelle Shipman, Dr Mark Elsegood, Emeritus Professor Bill Clegg, Professor Andrew Houlton

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Abstract

Dithioether- or diamine-tethered adenine derivatives react with PtII, PdII, and RhIII ions to give N3-coordinated complexes of the types [MCI(SSN)]+ (M = Pt or Pd), [RhCl3(SSN)], or [RhCl3(NNN)] (where SSN = 1-(N9-adenine)-3,6-dithia-heptane or 1-(N9-adenine)-4,7-dithia-octane; NNN = ethylenediamine-N,9-ethyladenine). Single-crystal X-ray analysis confirms the nature of the metal-nucleobase interaction and highlights a conserved intermolecular hydrogen-bonding motif for all the complexes, irrespective of the metal-ion geometry. Coordination significantly reduces the basicity of the adeninyl group, as indicated by a pKa value of -0.16 for [PtCl(N3-1-(N9-adenine)-3,6-dithia-heptane)]BF4, compared to a pKa value of 4.2 for 9-ethyladenine. The site of proton binding, N1 or N7, could not be unambiguously assigned from the 1H NMR data, because of the similar effect on the chemical shifts of the H2 and H8 protons. Density functional calculations at the BP-LACVP* level suggest N1 as the site of protonation for this type of complex. This is in contrast to the N7-protonation reported for [Pt(dien)(N3-6,6′,9-trimethyladenine)]2+, as reported elsewhere (Meiser et al., Chem. - Eur. J. 1997, 3, 388). However, further electronic structure calculations in the gas phase reveal that the preferred site for protonation for N3-bound complexes is conformationally dependent. N3 coordination was also found to reduce the extent of base pairing between adenine and thymine in dimethylsulfoxide for the self-complementary complex [PtCl(L3)]+ (L3 = 1-(N9-adenine)-3,6-dithia-9-(N1-thymine)nonane), compared to that for the uncomplexed ligand.


Publication metadata

Author(s): Amantia D, Price C, Shipman MA, Elsegood MRJ, Clegg W, Houlton A

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2003

Volume: 42

Issue: 9

Pages: 3047-3056

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic020657g

DOI: 10.1021/ic020657g

PubMed id: 12716200


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