Photoirradiated and. gamma. -ray-irradiated reactions of manganese(III, IV, V) tetraphenylporphyrins in 2-methyltetrahydrofuran. Reactions of azidomanganese(III) porphyrin

Journal Article · Wed Apr 22 04:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00255a018· OSTI ID:6558353

Jin, T; Suzuki, T; Imamura, T; Fujimoto, M

Manganese(III, IV) tetraphenylporphyrins Mn/sup III/(TPP)X(TPP = 5,10,15,20-tetraphenylporphinato; X = I, Br, Cl, N/sub 3/, NCS, OAc) and Mn/sup IV/(TPP)(OCH/sub 3/)/sub 2/ in 2-methyltetrahydrofuran (MeTHF) at room temperature were reduced to yield Mn/sup II/(TPP) by photoirradiation with visible light (440-750 nm) or by ..gamma..-ray irradiation. The photoirradiation of Mn/sup III/(TPP)N/sub 3/ in the rigid matrix at 77 K affords Mn/sup V/(TPP)N. Photochemically stable Mn/sup V/(TPP)N was reduced to Mn/sup II/(TPP) by ..gamma..-irradiation at room temperature. ..gamma..-irradiation of MeTHF solutions of Mn/sup III/(TPP)X at 77 K causes one-electron reduction to form the constrained complexes (Mn/sup II(TPP)X)/sup -/. Warming the matrices after ..gamma..-irradiation formed Mn/sup II/(TPP), liberating ligand X/sup -/. The near-infrared bands of Mn/sup III/(TPP)X red shift along with the shifts of the bands in the visible region by varying the ligand X. The characteristic bands of the constrained complex (Mn/sup II(TPP)X)/sup -/ in the near-infrared region red shift in the order X = Cl > Br > 1. The photoirradiation of Cr/sup III/(TPP)N/sub 3/ with visible light affords Cr/sup V/(TPP)N at room temperature and at 77 K. 39 references, 6 figures, 5 tables.

• Research Organization: Hokkaido Univ., Sapporo, Japan
• OSTI ID: 6558353
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:8; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500 -- Photochemistry
400600* -- Radiation Chemistry
ANTITHYROID DRUGS
AZIDES
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMISTRY
DRUGS
ELECTROMAGNETIC RADIATION
FURANS
GAMMA RADIATION
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HORMONE ANTAGONISTS
IONIZING RADIATIONS
MANGANESE COMPOUNDS
NITROGEN COMPOUNDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
TETRAHYDROFURAN
THIOCYANATES
TRANSITION ELEMENT COMPOUNDS
VISIBLE RADIATION