Photochemisty of low-spin iron(III) complexes with macrocyclic ligands
Journal Article
·
· Inorg. Chem.; (United States)
The charge-transfer photochemistries of Fe(TIM)(OCH/sub 3/)CH/sub 3/OH/sup 2 +/ and Fe(DMG)/sub 2/(OCH/sub 3/)CH/sub 3/OH can be described as a photooxidation of coordinated methanol and the reduction of the metal center. Reduction of Fe(TIM)(OCH/sub 3/)CH/sub 3/OH/sup 2 +/ by hydroxymethyl radicals (k = 1.9 x 10/sup 6/ M/sup -1/s/sup -1/) and the reoxidation of the Fe(II)-TIM product by dioxygen were investigated by flash photolysis. Quantum yields of the photolysis products were determined as a function of the excitation wavelength. Limiting yields phi/sub L/ = 4.0 x 10/sup -2/ for Fe(TIM)(OCH/sub 3/)CH/sub 3/OH/sup 2 +/ and phi/sub L/ = 7.0 x 10/sup -2/ for Fe(DMG)/sub 2/(OCH/sub 3/)CH/sub 3/OH were obtained for photonic energies larger than or equal to 76.3 kcal/mol. The photochemical properties of these complexes are attributed to the population of charge-transfer methoxy to iron(III) states.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 6535736
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:11; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMISTRY
COMPLEXES
DATA
EXPERIMENTAL DATA
GRAPHS
INFORMATION
IRON COMPLEXES
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
REACTION KINETICS
TABLES
TRANSITION ELEMENT COMPLEXES
400500* -- Photochemistry
CHEMISTRY
COMPLEXES
DATA
EXPERIMENTAL DATA
GRAPHS
INFORMATION
IRON COMPLEXES
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
REACTION KINETICS
TABLES
TRANSITION ELEMENT COMPLEXES