K. Coulter, A. Mcauley, S. Rettig
May 1, 2001
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0
Influential Citations
5
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Journal
Canadian Journal of Chemistry
Abstract
The pentadentate macrobicycle,14-thia-1,4,8,11-tetraazabicyclo[9.5.3]nonadecane (L1), has been synthesized by high dilution cyclization of 1-thia-4,8-diazacyclododecane ([10]aneN2S) (2) with N,N'-bis(α-chloro acetamido) propane (3) and subsequent reduction of the di-oxo intermediate. The structure of the [Ni(L1)(ClO4)](ClO4)·2[Ni(L1)(OH2)](ClO4)2·6H2O complex (monoclinic, P21/c, a = 13.9261(4) A, b = 30.279(2) A, c = 17.1248(3) A, β = 94.5065(3)°) at R = 0.039 (Rw = 0.034) for 911 parameters using 18 266 reflections with I > 3σI has been determined. The ligand adopts a trans-III configuration. The Ni(II) ion is pseudooctahedral with Ni-S = 2.3896(10) A in [Ni(L1)(ClO4)]+ and 2.4193(10) A, 2.4225(10) A, in the two [Ni(L1)(H2O)]2+ cations. Both nickel(II) and nickel(III) complexes are six-coordinate in solution. Oxidation of the [Ni(L1)(OH2)]2+ complex with K2S2O8 in aqueous solution yielded an ESR active Ni(III) species and the frozen solution spectrum displayed axial symmetry with g = 2.159 and g|| = 2.02...