Mixed Adenine/Guanine Quartets with Three trans-a(2)Pt(II) (a=NH3 or MeNH2) Cross-Links: Linkage and Rotational Isomerism, Base Pairing, and Loss of NH3

作者：Alberti Francisca M; Rodriguez Santiago Luis; Sodupe Mariona^*; Mirats Andrea; Kaitsiotou Helena; Sanz Miguel Pablo J; Lippert Bernhard

来源：Chemistry - A European Journal, 2014, 20(12): 3394-3407.

DOI：10.1002/chem.201304686

• adenine
• conformational change
• DFT calculations
• guanine
• metallacycles
• platinum

Of the numerous ways in which two adenine and two guanines (N9 positions blocked in each) can be cross-linked by three linear metal moieties such as trans-a(2)Pt(II) (with a=NH3 or MeNH2) to produce open metalated purine quartets with exclusive metal coordination through N1 and N7 sites, one linkage isomer was studied in detail. The isomer trans,trans,trans-[{Pt(NH3)(2)(N7-9-EtA-N1)(2)}{Pt(MeNH2)(2)(N7-9-MeGH)}(2)][(ClO4)(6)]3H(2)O (1) (with 9-EtA=9-ethyladenine and 9-MeGH=9-methylguanine) was crystallized from water and found to adopt a flat Z-shape in the solid state as far as the trinuclear cation is concerned. In the presence of excess 9-MeGH, a meander-like construct, trans,trans,trans-[{Pt(NH3)(2)(N7-9-EtA-N1)(2)}{Pt(MeNH2)(2)(N7-9-MeGH)(2)}][(ClO4)(6)][(9-MeGH)(2)]7H(2)O (2) is formed, in which the two extra 9-MeGH nucleobases are hydrogen bonded to the two terminal platinated guanine ligands of 1. Compound1, and likewise the analogous complex 1a (with NH3 ligands only), undergo loss of an ammonia ligand and formation of NH4+ when dissolved in [D-6]DMSO. From the analogy between the behavior of 1 and 1a it is concluded that a NH3 ligand from the central Pt atom is lost. Addition of 1-methylcytosine (1-MeC) to such a DMSO solution reveals coordination of 1-MeC to the central Pt. In an analogous manner, 9-MeGH can coordinate to the central Pt in [D-6]DMSO. It is proposed that the proton responsible for formation of NH4+ is from one of the exocyclic amino groups of the two adenine bases, and furthermore, that this process is accompanied by a conformational change of the cation from Z-form to U-form. DFT calculations confirm the proposed mechanism and shed light on possible pathways of this process. Calculations show that rotational isomerism is not kinetically hindered and that it would preferably occur previous to the displacement of NH3 by DMSO. This displacement is the most energetically costly step, but it is compensated by the proton transfer to NH3 and formation of U(-H+) species, which exhibits an intramolecular hydrogen bond between the deprotonated N6H(-) of one adenine and the N6H(2) group of the other adenine. Finally the question is examined, how metal cross-linking patterns in closed metallacyclic quartets containing two adenine and two guanine nucleobases influence the overall shape (square, rectangle, trapezoid) and the planarity of a metalated purine quartet.

• 出版日期2014-3-17