A spectral study of the interaction of dioxygen with sublimed layers of manganese(ii)meso-tetraphenylporphyrinate

Abstract

The low-temperature interaction of sublimed layers of manganese(tl) meso-tetraphenytporphyrinate (MnTPP) with O 2, which has previously been observed only in solutions and in an inert gas matrix, was found by electron absorption and IR spectroscopy. The coordination of 02 with sublimed MnTPP layers is only partially reversible. Bands that can serve as IR-spectral markers characteristic of the high-spin Mn II ion in MnTPP and its axial complexes were observed.

FTIR and optical spectroscopic studies of the reactions of heme models with nitric oxide and other NOx in porous layered solids

“…Similar reactivity is seen with the manganese(II) analog Mn(TPP) [65], but the cobalt(II) species Co(TPP) gave only the nitro complex Co(TPP)(NO 2 ) under the same experimental conditions [60,66]. The FTIR data clearly show that the NO 2 reaction with ferrous porphyrinato complexes proceeds via two distinct stages.…”

Nitric Oxide Dioxygenation by O2 Adducts of Manganese Porphyrins

“…Sublimed layers of Mn­(Por) (Por = TPP or TTP) were obtained on the cold (77 K) KBr support of an optical cryostat according to the published procedure . Thin layers of the metallo-tetraarylporphyrins sublimed onto a low T (77 K) surface are sponge-like and have high microporosity that allows potential ligands to diffuse easily across the bulk .…”

“…The species thus formed are convenient for spectroscopic studies due to absence of solvent interference. As previously described, the precursor complex Mn­(Por)­(L) was introduced into the Knudsen cell of the high vacuum system and heated at 490 K for ∼3 h until the vacuum gauge indicated complete dissociation of the axial ligand. The resulting Mn­(Por) was sublimed from the Knudsen cell at ∼520 K and deposited as layers on a cold KBr substrate of the optical cryostat.…”

A structurally-characterized peroxomanganese(iv) porphyrin from reversible O2 binding within a metal–organic framework

“…11 ) and thus form high-valent peroxomanganese complexes. 12 To date, one crystal structure of an O 2 coordinated to a manganese porphyrin has been reported. This complex, formed by addition of KO 2 to (TPP)Mn II (H 2 TPP = 5,10,15,20-tetraphenylporphyrin), was shown to feature a Mn III ion coordinated to a peroxo ligand in a side-on, η 2 binding mode.…”