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Synthesis and characterization of the cobalt complexes of new BF2+ bridged, anthracene substituted bis(α-dioxime) macrocycles.
Autorzy
Rok wydania
1991
Czasopismo
Journal of Coordination Chemistry
Numer woluminu
23
Strony
91-111
DOI
10.1080/00958979109408245
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The synthesis, characterization and structure are described for new cobalt complexes, with a BF2 + bridged, bis(a-dioxime) ligand, based upon a sterically demanding framework derived from an anthracene Diels-Alder adduct. The ligand provides a deep cleft within which axial ligands and/or O2 can bind. The crystal structures of the bis- and mono(BF2 +) bridged complexes have space groups P21/c and P I, respectively, with unit cell dimensions a = 12.662(2) Å, b = 16.430(3) Å, c = 10.438(3) Å, β = 103.51(2)°, a = 12.046(1)Å, b = I7.596(3)Å, c = 9.939(I)Å, a = 105.15(1)°, β = 102.87(1)°, and γ = 78.13(1), respectively. For both complexes Z = 2 and the residuals R and R w were 0.070, 0.104, and 0.059, 0.075, respectively. ESR studies show that the cobalt(II) complexes have a strong tendency to bind two axial nitrogen bases, adopting a coordination number of six. The dioxygen affinity of the new cobalt(II) dioxygen carrier is limited by the competition between axial base binding and O2 binding. This extends the understanding of correlations between electrode potentials and O2 affinities and possible sources of apparent contradictions.
Słowa kluczowe
Cobalt comple, xmacrocycle, dioxygen binding, ESR study, X-ray crystal structure
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