Reaction of the Five-Coordinate O-Nitrito Complex Fe(Por)(ONO) (Por = meso-tetra-arylporphyrinato) with THF Gives Two Six-Coordinate Isomers

Article

<< Previous

Next >>

Contents Vol 62(10)

doi:10.1071/CH09318

Reaction of the Five-Coordinate O-Nitrito Complex Fe(Por)(ONO) (Por = meso-tetra-arylporphyrinato) with THF Gives Two Six-Coordinate Isomers

Tigran S. Kurtikyan ^A ^B ^E, Astghik A. Hovhannisyan ^A, Alexei Iretskii ^C, Peter C. Ford ^D ^E

^A Molecule Structure Research Centre (MSRC) NAS, 0014, Yerevan, Armenia.
^B Research Institute of Applied Chemistry (ARIAC), 0053, Yerevan, Armenia.
^C Department of Chemistry, Lake Superior State University, Sault Ste Marie, MI 49783, USA.
^D Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106-9510, USA.
^E Corresponding authors. Email: kurto@netsys.am; ford@chem.ucsb.edu





	PDF (395 KB) $25



	Export Citation

Print

Australian Journal of Chemistry 62(10) 1226–1230 http://dx.doi.org/10.1071/CH09318
Submitted: 4 June 2009 Accepted: 24 July 2009 Published online: 13 October 2009

Abstract

The effect of the proximal ligand on the coordination of the nitrite ligand to the heme model systems Fe(Por)(η¹-ONO) (Por = meso-tetraarylporphyrinato dianion) was investigated by FTIR and UV-vis spectra in solvent free, low temperature, porous layered solids and by density functional computations. The reaction of the five-coordinate complex Fe(Por)(η¹-ONO) with the ether tetrahydrofuran gives a mixture of the O-nitrito and N-nitrito isomers Fe(Por)(THF)(η¹-ONO) and Fe(Por)(THF)(NO₂), respectively. This observation is in contrast to earlier studies with nitrogen donor Lewis bases where the N-nitrito isomers were clearly the more stable of the six-coordinated complexes. The adduct formation is reversible; the five-coordinate O-nitrito complexes Fe(Por)(η¹-ONO) were largely restored upon warming under vacuum pumping.