Reaction dynamics of photosubstitution intermediates of the triruthenium cluster Ru sub 3 (CO) sub 12 as studied by flash photolysis with infrared detection
- Univ. of California, Santa Barbara (USA)
The reaction dynamics of intermediates formed by 308-nm XeCl excimer-laser excitation of the triruthenium cluster Ru{sub 3}(CO){sub 12} in room-temperature isooctane solution were studied by using a flash-photolysis apparatus with a tunable infrared laser probe source and Hg/Cd/Te fast-risetime ir detector. The primary photoreaction is the dissociation of CO to give Ru{sub 3}(CO){sub 11}, which is rapidly trapped in second-order reactions by CO or by an added nucleophile such as tetrahydrofuran. The rate constants for such trapping are shown t be 2.4 {times} 10{sup 9} and 6.1 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1} for CO and THF, respectively. The intermediate Ru{sub 3}(CO){sub 11}(THF) reacts with CO to re-form Ru{sub 3}(CO){sub 12} via an apparent first-order dissociation of the THF with a rate constant about 2 {times} 10{sup 6} s{sup {minus}1}. The flash-photolysis apparatus with the ir detection system is described in detail. 17 refs., 6 figs.
- DOE Contract Number:
- FG03-85ER13317
- OSTI ID:
- 6985518
- Journal Information:
- Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:18; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
An investigation of coordinatively unsaturated metal carbonyls using time-resolved infrared spectroscopy
Photoreactions of the triruthenium cluster HRu sub 3 (CO) sub 10 (. mu. -COCH sub 3 ). Isomerization of the bridging alkylidyne ligand and competing ligand substitutions
Related Subjects
400500* -- Photochemistry
CARBONYLS
CHEMICAL REACTIONS
COMPLEXES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
INFORMATION
LASER RADIATION
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES