Photochemical studies as a function of solvent viscosity. A new photochemical pathway in the reaction of (η5-C5H4Me)2Mo2(CO)6 with CCl4Electronic supplementary information (ESI) available: plots of quantum yields vs. viscosity for the photolysis of Cp′2Mo2(CO)6 in hexane–squalane, hexane–paraffin oil, THF–polyglyme, and ethanol–propylene glycol; table of quantum yields showing dependence on [CCl4]; table of values of fitting parameters in eqn. (3). See http://www.rsc.org/suppdata/pp/b2/b202112a/
Braden, Dale A.; Parrack, Eileen E.; Tyler, David R.; Braden Dale A.; Department of Chemistry, University of Oregon; Parrack Eileen E.; Department of Chemistry, University of Oregon; Tyler David R.; Department of Chemistry, University of Oregon
Журнал:
Photochemical & Photobiological Sciences
Дата:
2002
Аннотация:
This paper reports the results of a study that used systematic changes in the solvent viscosity to probe the photochemical reactivity of the Cpâ ²2Mo2(CO)6 (Cpâ ² = η<sup>5</sup>-C5H4CH3) molecule. The quantum yields for photolysis of Cpâ ²2Mo2(CO)6 in the presence of CCl4 were studied as a function of solvent viscosity. The quantum yields did not decrease to zero with increasing solvent viscosity but rather leveled off at a constant, non-zero value. This result cannot be explained by any of the previously reported radical or Moâ CO dissociation photochemical pathways for this molecule, and therefore an additional photochemical pathway is suggested to be operating in the reaction. The new pathway may involve a reactive isomer of Cpâ ²2Mo2(CO)6 or possibly electron transfer between the excited state of Cpâ ²2Mo2(CO)6 and CCl4.
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