title: Interaction of nitrogen oxides with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II); IR evidence of oxo-transfer from (nitro)porphyrinatocobalt(III) to free nitric oxide.
abstract: Interaction of a low-pressure NO2 with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II) (Co(TPP)) leads to formation of 5-coordinate nitro complex Co(III)(TPP)(NO2). Upon exposure of these layers to pyridine vapors, the fast reaction with formation of 6-coordinate nitro-pyridine porphyrins (Py)Co(III)(TPP)(NO2) occurs. By means of IR spectroscopy and use of nitrogen oxide isotopomers, it is shown that an oxo-transfer reaction occurs from 5-coordinate species to free nitric oxide (NO) while the 6-coordinate complex is rather inert. It is also demonstrated that the stepwise addition of low-pressure NO2 to nitrosyl complex Co(TPP)(NO) leads to formation of the nitro complex most likely by an exchange reaction.
authors.affiliation: Molecular Structure Research Centre NAS, 375014 Yerevan, Armenia. tkurt@msrc.am
authors.forename: Tigran S
authors.initials: TS
authors.lastname: Kurtikyan
authors.forename: Arthur N
authors.initials: AN
authors.lastname: Mardyukov
authors.forename: John A
authors.initials: JA
authors.lastname: Goodwin