Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
17
pubmed:dateCreated
2005-4-27
pubmed:abstractText
The reaction(s) of nitric oxide (nitrogen monoxide) gas with sublimed layers containing the nitrato iron(III) complex Fe(III)(TPP)(eta(2)-O(2)NO) (1, TPP = meso-tetraphenyl porphyrinate(2)(-)) leads to formation of several iron porphyrin species that are ligated by various nitrogen oxides. The eventual products of these low-temperature solid-state reactions are the nitrosyl complex Fe(TPP)(NO), the nitro-nitrosyl complex Fe(TPP)(NO(2))(NO), and 1 itself, and the relative final quantities of these were functions of the NO partial pressure. It is particularly notable that isotope labeling experiments show that the nitrato product is not simply unreacted 1 but is the result of a series of transformations taking place in the layered material. Thus, the nitrato complex formed from solid Fe(TPP)(eta(2)-O(2)NO) maintained under a (15)NO atmosphere was found to be the labeled analogue Fe(TPP)(eta(2)-O(2)(15)NO). The reactivities of the layered solids are compared to the behaviors of the same species in ambient temperature solutions. To interpret the reactions of the labeled nitrogen oxides, the potential exchange reactions between N(2)O(3) and (15)NO were examined, and complete isotope scrambling was observed between these species under the reaction conditions (T = 140 K). Overall it was concluded from isotope labeling experiments that the sequence of reactions is initiated by reaction of 1 with NO to give the nitrato nitrosyl complex Fe(TPP)(eta(1)-ONO(2))(NO) (2) as an intermediate. This is followed by a reaction in the presence of excess NO that is equivalent to the loss of the nitrate radical NO(3)(*)( )()to give Fe(TPP)(NO) as another transient species. A plausible pathway involving NO attack on the coordinated nitrate of 2 resulting in the release of N(2)O(4) concerted with electron transfer to the metal center is proposed.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
May
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
4
pubmed:volume
127
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
6216-24
pubmed:dateRevised
2006-11-15
pubmed:meshHeading
pubmed:year
2005
pubmed:articleTitle
Reactions of nitrogen oxides with heme models. Spectral and kinetic study of nitric oxide reactions with solid and solute Fe(III)(TPP)(NO3).
pubmed:affiliation
Research Institute of Applied Chemistry (ARIAC), 375005, Yerevan, Armenia. tkurt@msrc.am
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't