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Resonance Raman spectra of dioxygen adducts of manganese(II) porphyrins in dioxygen matrices

โœ Scribed by A. Weselucha-Birczynska; L. M. Proniewicz; K. Bajdor; K. Nakamoto

Publisher
John Wiley and Sons
Year
1991
Tongue
English
Weight
436 KB
Volume
22
Category
Article
ISSN
0377-0486

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โœฆ Synopsis

The resonance Raman spectra of side-on type dioxygen adducts of Mn(TMP), Mn(TPP) and Mn(OEP), where TMP, TPP and OEP denote the dianions of tetramesityl-, tetraphenyland octaethyl-porphines, respectively, were measured in 0,-Ar(l:30) matrices at cu. 15 K. The bands near 990, 710 and 430 cm-' were assigned to v(O,), v,(MR-O) and v,(Mn-O), respectively, based on 1602/180t isotopic shifts and normal coordinate calculations on an isosceles MnO, moiety. Vibrational coupling between the vJMn-0) and porphyrin modes obscured the location of the former mode in the spectra of Mn(TPP)O, and Mn(OEP)O, The bands near 825 cm-* which appear in all three porphyrins are shifted 34-36 cm-' on '602/180t substitution. Evidence is presented to show that this band is due to the v(Mn=O) of oxomanganese(1V) porphyrin, which was produced by photo-cleavage of the 0-0 bond of the dioxygen adduct. These v(Mn=O) are cu. 70 cm-' higher than those observed in acetonitrile solution. This has been attributed to the difference in the spin state; the oxomanganese(1V) porphyrins in acetonitrile solution are of high spin whereas those produced in OrAr matrices are of low spin.

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