N. D. Villanueva, M. Chiang, J. Bocarsly
Feb 4, 1998
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Journal
Inorganic Chemistry
Abstract
We have derivatized the pendant amine of (5-amino-5-methyl-3,7-diaza-2,9-nonanedioato)chlorocopper(II) with 3-pyridinecarboxaldehyde and 4-pyridinecarboxaldehyde. These new complexes, along with the starting material, comprise a set of copper complexes with chemically identical inner coordination spheres that provide protonatable nitrogen attached to the ligand framework. The 3-pyridinecarboxaldehyde adduct has been characterized by X-ray crystallography. This complex crystallized in the space group P21/n with a = 12.025(8) A, b = 12.304(5) A, c = 13.311(8) A, β = 94.76(5)°, V = 1962(1) A3, and Z = 4 (R, Rw = 0.049; 0.045). pH-dependent changes in the electronic spectroscopy and electrochemistry of these complexes have been observed. The parent complex undergoes a ∼300 cm-1 shift in λmax and a +140 mV shift in midpoint potential on going from high pH to low pH, while the pyridinecarboxaldehyde Schiff-base derivatives undergo smaller changes (78 and 110 cm-1 and 104 and 100 mV, respectively). The origins o...