Abstract:
Reactions of 2, 2’- pyridil (pyCOCOpy) with CuCl2 center dot 2H(2)O and
CuBr2 in EtOH yielded the mononuclear [Cu( pyCOOEt)(2)Cl-2] center dot
H2O (1) and the one-dimensional, mixed-valence complex
[(Cu2CuII)-Cu-I( pyCOOEt)(2)Br-4] n (2), Both complexes crystallize in
the triclinic space group P <(1)over bar>. The lattice constants are a =
8.382( 2), b = 9.778( 2), c = 7.814 alpha = 101.17( 1), beta = 114.55(
1), gamma = 94.14( 1)degrees for 1 and a = 8.738( 1), b = 9.375( 2), c =
7.966( 1), alpha = 79.09( 1), beta = 64.25 gamma = 81.78( 1)degrees for
2. 2,2’- pyridil undergoes a metal-assisted alcoholysis and oxidation
leading to decomposition and yielding ethyl picolinate (pyCOOEt) ligand.
The autoredox process associated with the reduction of copper(II) to
copper( I) in the case complex 2 is discussed in terms of the increased
redox activity of the copper( II) bromide system relative to the copper(
II) system.
