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; Astghik A. Hovhannisyan; Alexei Iretskii; Peter C. Ford

doi:10.1071/CH09318

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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 and Peter C. Ford ^D ^E

+ Author Affiliations

- Author Affiliations

^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

Australian Journal of Chemistry 62(10) 1226-1230 https://doi.org/10.1071/CH09318
Submitted: 4 June 2009 Accepted: 24 July 2009 Published: 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.

Acknowledgements

Financial support from ISTC (Project #A-484) is gratefully acknowledged. P.C.F. also thanks the US National Science Foundation (CHE-0749524).

References

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

Abstract

Acknowledgements

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