Supramolecular Isomerism of 2,2′- Bipyrazine Complexes with cis-(NH3)2PtII: Ligand Rotational State and Sequential Orientation Determine the 3D Shape of Metallacycles

2,2'-Bipyrazine (2,2'-bpz) reacts with cis-(NH3)(2)Pt-II in water to give a variety of products, several of which were isolated and characterized by X-ray analysis: cis-[Pt(NH3)(2)(2,2'-bpz-N-4)(2)] (NO3)(2)center dot 3H(2)O (1), [{cis-Pt-(NH3)(2)(2,2'-bpz-N-4, N4')}(3)](PF6)(5)NO3 center dot 7H(2)O (2a), [{cis-Pt-(NH3)(2)(2,2'-bpz-N-4,N4')}(3)](BF4)(2)-(SiF6)(2)center dot 15H(2)O (2b), and [{cis-Pt-(NH3)(2)(2,2'-bpz-N-4,N4')}(4)](SO4)(4)center dot 22H(2)O (3). In 1, 2b, and 3 the 2,2'-bpz ligands adopt approximately C-2h symmetries, hence the two pyrazine halves are in trans orientation, whereas in 2a all three 2,2'-bpz bridges are approximately C-2v symmetric, with the pyrazine halves cis to each other. The topologies of the two triangular complexes 2a and 2b are consequently distinctly different, but nevertheless both cations act as hosts for anions. In 2a a PF6- and a NO3- anion are associated simultaneously with the +6 cation, whereas in 2b it is a BF4- anion and a water molecule, which are trapped in its cavity. There is no anion inclusion in case of the metallasquare 3. In principle, 3 can exist in a large number of stereoisomers, depending on the rotational states of the bridging 2,2'-bpz ligands. Isolation of a single rotamer form of 3 with C-2h symmetric 2,2'-bpz ligands and an overall meso form is proposed to be a consequence of a highly efficient self-assembly process that starts from the precursor 1 and reaction with two cis-(NH3)(2)Pt-II units. This process leads to the isolated rotamer of 3 regardless of whether two cations 1 in head-head form react with two cis-(NH3)(2)Pt-II, or whether the Delta enantiomer of the chiral head-tail form of 1 combines with its Lambda enantiomer through two cis-(NH3)(2)Pt-II entities.