PHOTOGENERATION OF MONOMERIC PORPHYRINS FROM THE (TETRAPHENYLPORPHYRIN)RH-IN(OCTAETHYLPORPHYRIN) DISSOCIATION OF THE RH-IN BOND - INVESTIGATION OF THEIR REACTIONS IN THE PICOSECOND-MICROSECOND TIME-DOMAIN

Authors
COUTSOLELOS AG DAPHNOMILI D SCHEIDT WR FERRAUDI G
Citation
Ag. Coutsolelos et al., PHOTOGENERATION OF MONOMERIC PORPHYRINS FROM THE (TETRAPHENYLPORPHYRIN)RH-IN(OCTAETHYLPORPHYRIN) DISSOCIATION OF THE RH-IN BOND - INVESTIGATION OF THEIR REACTIONS IN THE PICOSECOND-MICROSECOND TIME-DOMAIN, Inorganic chemistry, 37(8), 1998, pp. 2077
Citations number
22
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Inorganic chemistry → ACNP
ISSN journal
00201669
Volume
37
Issue
8
Year of publication
1998
Database
ISI
SICI code
0020-1669(1998)37:8<2077:POMPFT>2.0.ZU;2-O
Abstract
The dissociation of the metal-metal bond in mixed-metal porphyrin dime rs was investigated in the picosecond-microsecond time domain by 355 n m flash photolysis. The photogenerated metalloradicals, [(porphyrin)M- .] where M = Rh, In, Tl, undergo transformations with a first-or pseud o-first-order kinetics, k = 4.1 x 10(10) s(-1), into intermediates tha t can be scavenged with CH2Cl2. On a longer time scale, dependencies o f the reaction rate on the photolyte and metalloradical concentrations reveal that the secondary products undergo recombinations among thems elves and reactions with excess parent complex. The illustration shows the time-resolved spectra recorded in 355 nm flash irradiations of (T PP)Rh-In(OEP) in toluene.