Synthesis and NMR characterization of the cis and trans isomers of [Ptii(N9-adeH)2(pz)2] and X-ray crystallography of the trans isomer

Abstract

The reaction of tetrapyrazine Pt(II) with adenine under basic conditions yielded two products both disubstituted by adenine and bound in all cases to the N-9 nitrogen of adenine. Crystals amenable to X-crystallographic analysis were obtained for one product which was consequently identified as trans-[Pt^II(N⁹-adeH)₂(pz)₂](NO₃)₄·H₂O. The other product, though, was identified as the cis isomer based on extensive and comparative NMR structural studies whereby the two compounds were examined as both neutral and tetraprotonated species in solution. The major product of the reaction was unexpectedly the cis isomer, thus obtained in contrast to the trans effect, and the reason for this result is speculated on. Computational calculations using DFT at the B3LYP/TZVP-MARI-J level of theory provided the head-to-tail conformer as the overwhelmingly more stable species over the head-to-head conformer for both compounds whilst the trans product was found to be more stable than the cis. Thus the reaction does not follow a thermodynamic course and rather is kinetically controlled in concert with the speculated mode of reaction.