Structural and Electron Paramagnetic Resonance Studies of the Square Pyramidal to Trigonal Bipyramidal Distortion of Vanadyl Complexes Containing Sterically Crowded Schiff Base Ligands
1997; American Chemical Society; Volume: 36; Issue: 27 Linguagem: Inglês
10.1021/ic970868z
ISSN1520-510X
AutoresCharles R. Cornman, Katherine M. Geiser-Bush, Stephen P. Rowley, Paul D. Boyle,
Tópico(s)Metal complexes synthesis and properties
Resumo[N,N'-Ethylenebis(o-(tert-butyl-p-methylsalicylaldiminato)]oxovanadium(IV) (1), [N,N'-propanediylbis(o-(tert-butyl-p-methylsalicylaldiminato)]oxovanadium(IV) (2), bis(N-methylsalicylaldiminato)oxovanadium(IV) (3), bis(N-isopropyl-o-methylsalicylaldiminato)oxovanadium(IV) (4), and, bis(N-methyl-o-(tert-butyl-p-methylsalicylaldiminato)oxovanadium(IV) (5) were prepared and characterized by X-ray crystallography and EPR spectroscopy. Complexes 1 and 2 are best described as square pyramids, while complexes 3−5 are distorted trigonal bipyramids, demonstrating that oxovanadium(IV) complexes can readily adopt a trigonal bipyramidal geometry. All five compounds give nearly the same parallel hyperfine coupling constant (Az) regardless of the fact that the geometry about the vanadium changes from square pyramidal to trigonal bipyramidal. Crystal data for 1: space group P1̄, a = 7.9382(3) Å, b = 12.6749(7) Å, c = 13.8353(7) Å, α = 109.608(5)°, β = 96.552(5)°, γ = 96.589(5)°, Z = 2. Crystal data for 2: space group I41/a, a = 16.1895(6) Å, b = 16.1895(6) Å, c = 41.117(3) Å, Z = 16. Crystal data for 3: space group C2/c, a = 18.8230(17) Å, b = 7.5118(5) Å, c = 11.7460(10) Å, β = 112.229(7)°, Z = 4. Crystal data for 4: space group P21/c, a = 9.7086(6) Å, b = 11.4554(7) Å, c = 20.866(2) Å, β = 103.943(6)°, Z = 4. Crystal data for 5: space group Pbca, a = 10.667(3) Å, b = 25.549(5) Å, c = 18.322(4) Å, Z = 8.
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