Reaction of the Five-Coordinate O-Nitrito Complex Fe(Por)(ONO) (Por = meso-tetra-arylporphyrinato) with THF Gives Two Six-Coordinate Isomers
2009; CSIRO Publishing; Volume: 62; Issue: 10 Linguagem: Inglês
10.1071/ch09318
ISSN1445-0038
AutoresTigran S. Kurtikyan, Astghik A. Hovhannisyan, Alexei V. Iretskii, Peter C. Ford,
Tópico(s)Hemoglobin structure and function
ResumoThe 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.
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