Stepwise Complexation of Ni(II) and Cu(II) Ions by 6,6'-C-spirobi(cyclam) (cyclam = 1,4,8,11-Tetraazacyclotetradecane), L(1). Syntheses and Redox Chemistry of [M(H(2)L(1))]X(4) (M = Cu(2+), Ni(2+)), [Cu(2)(L(1))]X(4), and [CuNi(L(1))]X(4) (X = ClO(4)(-)) and the X-ray Crystal Structure of [Cu(2)(L(1))](ClO(4))(4).
In aqueous HClO(4), the cation [H(4)(L(1))](4+) where L(1) is 6,6'-C-spirobi(cyclam) (cyclam = 1,4,8,11-tetraazacyclotetradecane), complexes Cu(2+) and Ni(2+) ions in a stepwise fashion to form [M(H(2)L(1))](ClO(4))(4) (M = Cu(2+) and Ni(2+)) from which [CuNi(L(1))](ClO(4))(4) has been prepared selectively. The preparation and the structure of [Cu(2)(L(1))](ClO(4))(4) (empirical formula, C(19)H(44)N(8)Cu(2)Cl(4)O(16); space group, triclinic; P&onemacr;; a = 8.1815(6) Å, b = 12.6098(9) Å, c = 16.6565(12) Å, alpha = 80.3890(10) degrees, beta = 76.5840(10) degrees, gamma = 87.1750(10) degrees, V = 1647.9(2) Å(3), and Z = 2; of the 9531 total reflections collected, 6779 reflections with I > 2sigma(I) on least-squares refinement provided final R(1) = 0.0657 and wR(2) = 0.1424) are also reported. The cyclic voltammograms (1.0 M NaCl, 0.1 M H(+); Pt electrodes; all E(1/2) vs NHE) of [M(H(2)L(1))](4+) (M = Cu(2+) and Ni(2+)) ions show single waves for the Cu(II)/Cu(III) couple (E(1/2) = 0.79 V, irreversible) and the Ni(II)/Ni(III) couple (E(1/2) = 0.56 V, reversible), respectively. In CH(3)CN (0.1 M Et(4)NClO(4)), the [Cu(2)(L(1))](4+) ion shows a reversible wave for the Cu(II)-Cu(II)/Cu(II)-Cu(III) couple ((1)E(1/2) = 1.120 V) and an irreversible wave for the Cu(II)-Cu(III)/Cu(III)-Cu(III) couple ((2)E(1/2) = 1.430 V). Similarly, a reversible wave for the Cu(II)-Ni(II)/Cu(II) -Ni(III) couple ((1)E(1/2) = 0.750 V) and an irreversible wave for the Ni(III)-Cu(II)/Ni(III)-Cu(III) couple ((2)E(1/2) = 1.20 V) are observed in the case of the [Cu(II)Ni(II)(L(1))](4+) ion. The [Cu(2)(L(1))](4+) ion (g( perpendicular) = 2.120, g( parallel) = 2.256 and 2.196, A( parallel) = 150 G, and D( parallel) = 75 G) and the mixed valent species [Cu(II)Ni(III)(L(1))](5+) (for Cu(2+), g( perpendicular) = 2.060, g( parallel) = 2.219, and A( parallel) = 100 G; for Ni(3+) in sulfate media, g( perpendicular) = 2.204 and g( parallel) = 1.967) and [Cu(II)Cu(III)(L(1))](5+) (g(xx)() = 1.982, g(yy)() = 2.155, g(zz)() = 2.386, A(yy)() = 80 G, and A(zz)() = 120 G) show dipolar-dipolar interaction. In the mixed-valent ions, due to strong electrostatic repulsion from either the Ni(III) or Cu(III) ions, significantly smaller A( parallel) (or A(zz)()) values are observed for the Cu(2+) ion compared to 200 G in the mononuclear ions. Also, the [Cu(II)Ni(II)(L(1))](4+) in aqueous HClO(4) and the [Ni(2)(L(1))](4+) ion in CH(3)NO(2) show a tendency to reduce perchlorate very slowly.
McAuley
A.
A
Department of Chemistry, Saint Mary's University, Halifax, Nova Scotia, Canada B2H 3C3.
Subramanian
S.
S
Zaworotko
M. J.
MJ
Biradha
K.
K