"Directed" assembly of metallacalix[n]arenes with pyrimidine nucleobase ligands of low symmetry: interchanging metals in mixed-metal metallacalix[4]arenes and incorporating additional metals at the exocyclic groups

Abstract

The pyrimidine (pym) nucleobase cytosine (H(2)C) forms cyclic ring structures ("metallacalix[n]arenes") when treated with square-planar cis-a(2)M(II) entities (M=Pt, Pd; a=NH(3) or a(2)=diamine). The number of possible linkage isomers for a given n and the number of possible rotamers can be substantially reduced if a "directed" approach is pursued. Hence, two cytosine ligands are bonded in a defined way to a kinetically robust platinum corner stone. In the accompanying paper (Part I: A. Khutia, P. J. Sanz Miguel, B. Lippert, Chem. Eur. J. 2010, 17, DOI: 10.1002/chem.2010002722) we have demonstrated this principle by allowing cis-[Pta(2)(H(2)C-N3)(2)](2+) to react with (en)Pd(II) to give cycles of (N1,N3⋅N3,N1▪)(x) (with x=2 or 3; ⋅ represents Pt(II) and ▪ represents Pd(II)). In an extension of this work we have now prepared cis-[Pta(2)(HC-N1)(2)] (1; HC=monoanion of cytosine) and treated it with (bpy)Pd(II) (bpy=2,2'-bipyridine) to give the Pt(2) Pd(2) cycle cis-[{Pt(NH(3))(2)(N1-HC-N3)(2)Pd(bpy)}(2)](NO(3))(4) ⋅13H(2)O (5) with the coordination sites of the metals inverted; hence, platinum is bonded to N1 and palladium is bonded to N3 sites. Again, not only the expected single linkage isomer is formed, but at the same time the solid-state structure and (1)H NMR spectroscopy reveal the preferential occurrence of a single rotamer (1,3-alternate). The addition of (bpy)Pd(II) to 5 led to the formation of Pd(6) Pt(2) complex 6 in which the exocyclic N4H(2) groups of the cytosine ligands have undergone deprotonation and chelate four more (bpy)Pd(II) entities through the O2 and N4H sites. With a large excess of (bpy)Pd(II) over 5 (4:1), cis-(NH(3))(2) Pt(II) is eventually substituted by (bpy)Pd(II) to give the Pd(8) complex 7. In both 6 and 7 stacks of three (bpy)Pd(II) entities occur. The linkage isomer of 5,cis-[{Pt(NH(3))(2)(N3-HC-N1)(2)Pd(bpy)}(2)](NO(3))(4) ⋅9H(2)O (8), has been structurally characterized and the two complexes compared. The acid/base properties of cis-[Pt(NH(3))(2)(H(2)C-N1)(2)] (1) have been determined and compared with those of the corresponding N3 isomer. The complexation of AgCl by 1 is reported.