4 years ago

Seven-coordinate tetraoxolate complexes

Seven-coordinate tetraoxolate complexes
The reaction of TPypA (tris(2-pyridylmethyl)amine) and Fe(BF4)2 and sodium nitraniIate (Na2 1NO2 ) or Mn(O2CMe)2 with chloranilic acid (H2 1Cl ) respectively forms [FeIII(TPyA)1NO2 ]2O and MnII(TPyA)1Cl , respectively. The structures of these 7-coordinate compounds have been determined. The former is a dinuclear FeIII compound possessing equivalent Fe(III) sites, and the latter forms a 1-D zigzag chain based upon the two bridging 1NO2 2− ions. The isomer shift and quadrupole splitting of the 57Fe Mössbauer spectra of [Fe(TPyA)1NO2 ]2O are consistent binuclear seven-coordinate high-spin FeIII state. Below 35 K a single quadrupole doublet split onto two doublets of equal intensities and equal isomer shifts as a result of structural non-equivalency of two iron sites within a dimer. The magnetic properties of [FeIII(TPyA)1NO2 ]2O can be fit the a homonuclear S = 5/2 ± 5/2 dinuclear spin model with strong intradimer antiferromagnetic coupling of J/k B  = −146 K (−101 cm−1) and g = 2.00, and interdimer coupling of θ = −5 K (H = −2JSa·Sb). MnII(TPyA)1Cl can be fit the a homonuclear S = 5/2 1-D Fisher chain expression with weak intrachain antiferromagnetic coupling with J/k B  = −0.33 K (−0.23 cm−1) and g = 2.06.

Publisher URL: www.sciencedirect.com/science

DOI: S0277538717306770

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