Nitrosyl porphyrins electronic structure

A large number of paramagnetic transition metal nitrosyl complexes have been studied using electron spin resonance (ESR) spectroscopy. Information on the electronic ground state can be derived from the g-value and the hyperfine coupling constants, and many [MLslNO)]" (see Table IV) and nitrosyl porphyrin complexes (99) have been studied in this way with a view to understanding their electronic structures. 

Mossbauer Spectroscopy. Mdssbauer spectroscopy has been used as a powerful technique to probe the electronic structure of the five- and six-coordinate ferrous nitrosyl porphyrins. The isomer shifts of both types of complexes (5 0.35 mm s ) are similar and show temperature dependences that are consistent with a second-order Doppler effect, but are slightly smaller than those of most other iron(II) porphyrin complexes (5 0.45 mm Unlike the isomer... 

Scheidt WR, Barabanschikov A et al (2010) Electronic structure and dynamics of nitrosyl porphyrins. Inorg Chem 49 6240-6252... 

So far, we have encountered the spin density as a variable both in the description of electronic structures of open-shell character and in the analysis of local quantities such as local spins or bond orders. For an accurate treatment of open-shell molecules, spin-spin interactions and chemical bonding, reliable spin densities are thus mandatory. However, the determination of rehable spin density distributions can be a difficult task in quantum chemistry [199, 200]. Examples of such difficult cases are iron nitrosyl complexes containing salen or porphyrin ligands for which DFT spin densities considerably depend on the approximate exchange-correlation functional [87,199]. 

In summary, the mechanism of reductive nitrosylation of Co porphyrins differs completely from the one observed for Fe analogues. It seems that the main reason for such a different reactivity behavior of Fe and Co porphyrins can be accounted for in terms of the h h instability of the [Co (P)(NO) (H2O)] intermediate. Although the electronic structure of the latter complex may have some contribution from the [Co (P)(NO )(H20)] structure, its instabUity prevents any further reaction with nucleophiles. This is in contrast to the mechanism of reductive nitrosylation of Fe(III) porphyrins, where general base catalysis involving a relatively stable [Fe (P)NO ] complex was observed. 

It is quite evident that the ferrous complexes of porphyrins, both natural and synthetic, have extremely high affinities towards NO. A series of iron (II) porphyrin nitrosyls have been synthesized and their structural data [11, 27] revealed non-axial symmetry and the bent form of the Fe-N=0 moiety [112-116]. It has been found that the structure of the Fe-N-O unit in model porphyrin complexes is different from those observed in heme proteins [117]. The heme prosthetic group is chemically very similar, hence the conformational diversity was thought to arise from the steric and electronic interaction of NO with the protein residue. In order to resolve this issue femtosecond infrared polarization spectroscopy was used [118]. The results also provided evidence for the first time that a significant fraction (35%) of NO recombines with the heme-Fe(II) within the first 5 ps after the photolysis, making myoglobin an efficient N O scavenger. 

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