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Optical and ESR studies for the reaction of molybdenum tetraphenylporphyrins in. gamma. -ray-irradiated 2-methyltetrahydrofuran

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00191a018· OSTI ID:6009392
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The molybdenum(V) tetraphenylporphyrins, Mo/sup V/O(TPP)X (X = NCS, F, Cl, Br), in the glassy matrix of 2-methyl-tetrahydrofuran (MeTHF) at 77 K are reduced by ..gamma..-ray irradiation to form the constrained complexes, (Mo/sub IV/O(TPP)X)/sup -/, in which the ligand X is forced to be coordinated to the central molybdenum. When the solution is warmed, Mo/sup IV/O(TPP) is formed by release of the ligand X. The bands of the visible absorption spectra of (Mo/sup IV/O(TPP)X)/sup -/ formed in the rigid matrix depend on the ligand X and shift to longer wavelengths in the order of X = F < NCS < Cl < Br. The formation of the complex of MeTHF, Mo/sup IV/O(TPP)MeTHF, was also detected as the temperature of the solution of Mo/sup IV/O(TPP) was lowered to -72/sup 0/C. The velocity of the backward reaction of Mo/sup IV/O(TPP) to form Mo/sup V/O(TPP)X is dependent on the ligand X. 30 references, 2 figures, 1 table.
Research Organization:
Hokkaido Univ., Sapporo, Japan
OSTI ID:
6009392
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:23; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ABSORPTION SPECTROSCOPY
ANTITHYROID DRUGS
AROMATICS
BROMIDES
BROMINE COMPOUNDS
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COMPARATIVE EVALUATIONS
COMPLEXES
CORRELATIONS
DATA
DATA ANALYSIS
DRUGS
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
FURANS
GAMMA RADIATION
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HORMONE ANTAGONISTS
INFORMATION
IONIZING RADIATIONS
KINETICS
LIGANDS
LOW TEMPERATURE
MAGNETIC RESONANCE
MATHEMATICAL MODELS
MEDIUM TEMPERATURE
MOLYBDENUM BROMIDES
MOLYBDENUM CHLORIDES
MOLYBDENUM COMPLEXES
MOLYBDENUM COMPOUNDS
MOLYBDENUM FLUORIDES
MTHF
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SOLVENTS
ORGANIC SULFUR COMPOUNDS
PORPHYRINS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
REDUCTION
REFRACTORY METAL COMPOUNDS
RESONANCE
SOLVENTS
SPECTROSCOPY
STABILITY
STRUCTURAL CHEMICAL ANALYSIS
SUPEROXIDE RADICALS
TEMPERATURE DEPENDENCE
TETRAHYDROFURAN
THIOCYANATES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS