Synthesis, characterization, and reactivity of iron(III) complexes supported by a trianionic ONO(3-) pincer ligand. Academic Article uri icon

abstract

  • Synthetic and characterization results of a new family of Fe(III) compounds stabilized by a trianionic [CF3-ONO](3-) pincer-type ligand are reported. The ligand possesses three negatively charged donors constrained to the meridional positions that provide sufficient electron density to stabilize high-valent metal complexes. Using the redox-insulated [CF3-ONO](3-), pentacoordinated square-pyramidal {[CF3-ONO]FeCl2}{LiTHF2}2 (3), dimeric -DME{[CF3-ONO]FeDME}2 (4), trigonal bipyramidal [CF3-ONO]Fe(bpy) (5), and octahedral [CF3-ONO]Fe(bpy)H2O (5H2O) complexes are synthesized. An interesting feature of the [CF3-ONO](3-) pincer-type ligand is its ability to coordinate the metal center in both the more common meridional positions or occupying a face of a trigonal bipyramidal complex. The molecular structure of 3 contains structural features similar to those of a rare square-planar high-spin Fe(II) complex, and the important role of the counterions in stabilizing a square-plane is emphasized. SQUID magnetometry measurements of 3 reveal its high-spin character, and cyclic voltammetry measurements indicate high oxidation state species are unstable. However, all compounds can be reduced, and in particular 5 displays a reversible reduction event at -2255 mV versus ferrocene (Fc(+)/Fc) that can be assigned to either the Fe(I)/Fe(0) couple or 2,2'-bipyridine reduction.

published proceedings

  • Inorg Chem

altmetric score

  • 1.75

author list (cited authors)

  • Pascualini, M. E., Di Russo, N. V., Quintero, P. A., Thuijs, A. E., Pinkowicz, D., Abboud, K. A., ... Veige, A. S.

citation count

  • 9

complete list of authors

  • Pascualini, Matias E||Di Russo, Natali V||Quintero, Pedro A||Thuijs, Annaliese E||Pinkowicz, Dawid||Abboud, Khalil A||Dunbar, Kim R||Christou, George||Meisel, Mark W||Veige, Adam S

publication date

  • November 2014