Issue 6, 1994

Synthesis, characterization and structure of the highly sterically congested complex (3,14-dimethyl-14-nitromethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docos-2-ene)nickel diperchlorate and structure of (3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docosa-2,13-diene)nickel diperchlorate

Abstract

The reaction of the diimine complex [NiL1][ClO4]2(L1= 3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docosa-2,13-diene), containing cyclohexane subunits fused to the five-membered chelate rings, with nitromethane in the presence of triethylamine produced the highly sterically congested complex [NiL2][ClO4]2(L2= 3,14-dimethyl-14-nitromethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docos-2-ene) containing one nitromethyl pendant arm. The electronic spectrum of [NiL2]2+ in nitromethane solution shows the d–d band at ca. 490 nm (ε= 170 dm3 mol–1 cm–1). The wavelength and the molar absorption coefficient are extraordinarily longer and larger, respectively, than those for square-planar nickel(II) complexes of L1 and other related 14-membered polyaza macrocycles. The crystal structures of [NiL1][ClO4]2 and [NiL2][ClO4]2 revealed that the former has normal square-planar geometry with the nickel atom lying on the N4 plane, whereas the latter has a severely distorted square-planar geometry with the metal atom 0.118 Å out of the mean plane of the donor nitrogen atoms. The steric effects of the substituents of the complexes on the geometry and the spectra are discussed. Crystal data: for [NiL1][ClO4]2, monoclinic, space group P21/n, a= 10.423(3), b= 8.9375(6), c= 13.457(3)Å, β= 94.459(12)°, Z= 2, R= 0.056 and R′= 0.057 for 2349 independent reflections with Fo2 > 3σ(Fo2); for [NiL2][ClO4]2, monoclinic, space group P21/n, a= 11.968(3), b= 12.6208(14), c= 19.358(6)Å, β= 105.008(1 5)°, Z= 4, R= 0.046 and R′= 0.045 for 3382 independent reflections with Fo2 > 3σ(Fo2).

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1994, 853-857

Synthesis, characterization and structure of the highly sterically congested complex (3,14-dimethyl-14-nitromethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docos-2-ene)nickel diperchlorate and structure of (3,14-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docosa-2,13-diene)nickel diperchlorate

S. Kang, M. Kim, D. Whang and K. Kim, J. Chem. Soc., Dalton Trans., 1994, 853 DOI: 10.1039/DT9940000853

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