Manganese(II), Iron(II), Cobalt(II), and Copper(II) Complexes of an Extended Inherently Chiral Tris-Bipyridyl Cage

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L') of type$[ML](PF_{6})_{2}(solvent)_{n}$and [FeL'](ClO₄)₂ are reported, where L is the hexa-tertiary butyl-substituted derivative of L'. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L' are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL]²⁺ and [FeL]²⁺ are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends ≈22 Å along the axial length of each complex. In contrast, [MnL]²⁺ and [FeL]²⁺ have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL']²⁺, the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy.