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Preceding cyclovoltammetric measurements of tetra(2-pyridyl)pyrazine (TPP) in aprotic THF solution and the lowering of the reduction potential on Li + [B(C 6 H 5 ) 4  ] addition, the crystallization of diprotonated [TPPH 2  ++ ][B(C A H 5 ) 4  - ] 2  and of [2,4,6-tris(2-pyridyl)-1,3,5- triazine(Li + )][B(C 6 H 5 ) 4  - ] have stimulated the preparation and structural characterization of the following (TPP) 1,2  copper(II) and (TPP) 2  nickel(II) salts: (1) Green TTP-copper(II)- dichlorideacetonitrile with Cu 2+  fivefold coordinated by three N contacts to one TPP ligand and by two Cl anions, (2) green di(TPP)-copper(II)-di(perchlorate)·2 acetonitrile with fully encapsulated Cu 2+  coordinated to six N centers of two TPP ligands, and (3) the analogous nickel(II) complex, brown di(TPP)-nickel(II)-bis-(tetrafluoroborat)·3 water-methanol. Both complexes [(TPP)Me 2+ (TPP)](X - ) 2  with the Me 2+  dications in the cavity provided by two twisted TPP ligands are reported for the first time. The discussion of the crystal structures is based on an extensive search in the Cambridge Structural Database, which confirms the distortion mode around the penta-coordinated Cu 2+  center, and a more strongly distorted octahedron at the Cu 2+  center relative to that at the six-coordinate Ni 2+  center as well as shorter contacts Me 2+  ··· N to the pyrazine N centers than to the pyridine N centers. The comparison of the monodentate terpyridyl ligand with the bidentate tetra(2-pyridyl)pyrazine suggests the preparation of Me +n -bridged polymer chains terminated by terpyridyl complexation.

zeitschrift für naturforschung b

Wechselwirkungen in Kristallen, 112 [1]. Tetra(2-pyridyl)pyrazin - ein vielseitiger Ligand für Lewis-Säuren: Halb- und doppelschalige Komplexe von Kupfer(II)- und Nickel(II)-Salzen / Interactions in Crystals, 112 [1]. Tetra(2-pyridyl)pyrazine - a Versatile Ligand for Lewis Acids: Semi- and Doubly-Encapsulated Complexes of Copper(II) and Nickel(II) Salts