TY - JOUR
T1 - Synthesis, Cyclic Voltammetry, and X-ray Crystal Structures of Copper(I) and Copper(II) Complexes of Tris((6-phenyl-2-pyridyl)methyl)amine (TPPA)
AU - Chuang, Chang Lin
AU - Lim, Kitae
AU - Chen, Qiu
AU - Zubieta, Jon
AU - Canary, James W.
PY - 1995/5/1
Y1 - 1995/5/1
N2 - The synthesis and characterization of a new ligand, tris((6-phenyl-2-pyridyl)methyl)amine (TPPA) and some of its copper complexes are described. The complexes [Cu(TPPA)]BPh4 (7) and [Cu(TPPA)(AN)](ClO4)2 (8) (AN = acetonitrile) were prepared and their X-ray crystal structures and redox potentials were determined. The X-ray structure of 7 (triclinic space group, P1; a = 14.603(3), b = 15.137(3), c = 12.974(3) Å, α = 91.76(3), β = 105.87(3), γ = 117.00(3)°, V = 2417.4(12) Å3, Z = 2) displays a copper(I) atom with a distorted trigonal pyramidal coordination sphere, but the X-ray structure of 8 (triclinic space group, P1; a = 13.458(3), b = 13.586(3) c = 11.082(2) Å, α = 113.00(3), β = 94.48(3), γ = 90.53(3)°, V = 1857.7(9) Å3, Z = 2) indicates that the copper(II) atom has the expected trigonal bipyramid geometry. The reduction potential of 8 in dimethylformamide, dimethylacetamide, acetonitrile, and isobutyronitrile is quite positive compared to [Cu(TPA)](ClO4)2 (TPA = tris(2-pyridylmethyl)amine) under identical conditions. The various factors that may contribute to the difference in oxidation potential are discussed. The positive redox potential combined with steric factors accounts for the lack of reactivity of [Cu(TPPA)]PF6 with molecular O2.
AB - The synthesis and characterization of a new ligand, tris((6-phenyl-2-pyridyl)methyl)amine (TPPA) and some of its copper complexes are described. The complexes [Cu(TPPA)]BPh4 (7) and [Cu(TPPA)(AN)](ClO4)2 (8) (AN = acetonitrile) were prepared and their X-ray crystal structures and redox potentials were determined. The X-ray structure of 7 (triclinic space group, P1; a = 14.603(3), b = 15.137(3), c = 12.974(3) Å, α = 91.76(3), β = 105.87(3), γ = 117.00(3)°, V = 2417.4(12) Å3, Z = 2) displays a copper(I) atom with a distorted trigonal pyramidal coordination sphere, but the X-ray structure of 8 (triclinic space group, P1; a = 13.458(3), b = 13.586(3) c = 11.082(2) Å, α = 113.00(3), β = 94.48(3), γ = 90.53(3)°, V = 1857.7(9) Å3, Z = 2) indicates that the copper(II) atom has the expected trigonal bipyramid geometry. The reduction potential of 8 in dimethylformamide, dimethylacetamide, acetonitrile, and isobutyronitrile is quite positive compared to [Cu(TPA)](ClO4)2 (TPA = tris(2-pyridylmethyl)amine) under identical conditions. The various factors that may contribute to the difference in oxidation potential are discussed. The positive redox potential combined with steric factors accounts for the lack of reactivity of [Cu(TPPA)]PF6 with molecular O2.
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U2 - 10.1021/ic00114a013
DO - 10.1021/ic00114a013
M3 - Article
AN - SCOPUS:0000774001
SN - 0020-1669
VL - 34
SP - 2562
EP - 2568
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 10
ER -