158101-06-5Relevant academic research and scientific papers
Time-resolved infrared spectral studies of intermediates formed in the laser flash photolysis of Mn(CO)5CH3
Boese, William T.,Ford, Peter C.
, p. 3525 - 3531 (1994)
Laser flash photolysis (308 nm) of Mn(CO)5CH3 (I) in different solvents leads predominantly to CO photodissociation and the formation of reactive intermediates formulated as the solvente complexes cis-Mn(CO)4(solv)CH3. 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)4(solv)CH3 with CO displays second-order kinetics with a rate constant kCO nearly 8 orders of magnitude larger for solv = perfluoro-(methylcyclohexane) than for solv = tetrahydrofuran. The kL values for the second-order reaction of cis-Mn(CO)4(solv)CH3 in cyclohexane with various ligands L follow the approximate order 4-phenylpyridine ≈ H2O ≈ THF > P(OMe)3 ≈ PPh3 ≈ CO ≈ N2. 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)5(COCH3) (II) (Organometallics, 1993, 12, 4739-4741), and this comparison is used to substantiate the earlier conclusion that CO dissociation from II in weakly coordinating solvents leads to an η2-acyl-coordinated intermediate rather than to a solvento complex.
