TY - JOUR
T1 - The influence of phenyl substituents on the redox potentials of sterically hindered tripodal ligand/copper complexes
AU - Chuang, Chang Lin
AU - Lim, Kitae
AU - Canary, James W.
N1 - Funding Information:
We thank the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this work.
PY - 1995/5/1
Y1 - 1995/5/1
N2 - The structural characterization of Cu(I) and Cu(II) complexes of tris(6-phenyl-2-pyridylmethyl)amine (tppa), a derivative of the known tris(2-pyridylmethyl)amine (tpa), was recently reported. The phenyl substituents in [Cu(tppa)AN](ClO4)2 stabilize the Cu(I) state by 300–480 mV relative to [Cu(tpa)AN](ClO4)2. Reported here is the synthesis of the compounds bis(2-pyridylmethyl)-6-phenyl-2-pyridylmethylamine (Phtpa) and bis(6-phenyl-2-pyridylmethyl)-2-pyridylmethylamine (Ph2tpa) and the synthesis and cyclic voltammetry studies of their Cu(II) perchlorate complexes. The mechanism by which the phenyl groups increase the redox potential was found to be solvent-dependent: in AN, the increase in potential is primarily due to reduced local dielectric; in IBN, DMF, and DMA, the steric interaction between coordinated solvent and the phenyl substituents becomes important. The redox behavior of these complexes is consistent with anticipated modes of binding of solvent molecules in the inner sphere of the Cu(II) complexes.
AB - The structural characterization of Cu(I) and Cu(II) complexes of tris(6-phenyl-2-pyridylmethyl)amine (tppa), a derivative of the known tris(2-pyridylmethyl)amine (tpa), was recently reported. The phenyl substituents in [Cu(tppa)AN](ClO4)2 stabilize the Cu(I) state by 300–480 mV relative to [Cu(tpa)AN](ClO4)2. Reported here is the synthesis of the compounds bis(2-pyridylmethyl)-6-phenyl-2-pyridylmethylamine (Phtpa) and bis(6-phenyl-2-pyridylmethyl)-2-pyridylmethylamine (Ph2tpa) and the synthesis and cyclic voltammetry studies of their Cu(II) perchlorate complexes. The mechanism by which the phenyl groups increase the redox potential was found to be solvent-dependent: in AN, the increase in potential is primarily due to reduced local dielectric; in IBN, DMF, and DMA, the steric interaction between coordinated solvent and the phenyl substituents becomes important. The redox behavior of these complexes is consistent with anticipated modes of binding of solvent molecules in the inner sphere of the Cu(II) complexes.
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U2 - 10.1080/10610279508029886
DO - 10.1080/10610279508029886
M3 - Article
AN - SCOPUS:84972865128
SN - 1061-0278
VL - 5
SP - 39
EP - 43
JO - Supramolecular Chemistry
JF - Supramolecular Chemistry
IS - 1
ER -