Time-resolved infrared spectral studies of intermediates formed in the laser flash photolysis of Mn(CO){sub 5}CH{sub 3}
- Univ. of California, Santa Barbara, CA (United States)
Laser flash photolysis (308 nm) of Mn(CO){sub 5}CH{sub 3} (I) in different solvents leads predominantly to CO photodissociation and the formation of reactive intermediates formulated as the solvento complexes cis-Mn(CO){sub 4}(solv)CH{sub 3}. This conclusion is based upon the solvent sensitivity of the time-resolved infrared spectra and the dynamics of reactions with various ligands. For example, the reaction of cis-Mn(CO){sub 4}(solv)CH{sub 3} with CO displays second-order kinetics with a rate constant k{sub co} nearly 8 orders of magnitude larger for solv = perfluoro-(methylcyclohexane) than for solv = tetrahydrofuran. The k{sub l} values for the second-order reaction of cis-Mn(CO){sub 4}(solv)CH{sub 3} in cyclohexane with various ligands L follow the approximate order 4-phenylpyridine H{sub 2}O THF > P(OMe){sub 3} PPh{sub 3} > CO N{sub 2}. The quantitative behaviors of intermediates seen in the flash photolysis of I are compared with those seen in similar studies of the acetyl complex Mn(Co){sub 5}(COCH){sub 3} (II). 24 refs., 6 figs., 2 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG03-85ER13317
- OSTI ID:
- 102775
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 9 Vol. 13; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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