Computer Science
Scientific paper
Jun 2009
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..conferb06d&link_type=abstract
"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec
Computer Science
Radicals And Ions
Scientific paper
The construction of a custom fabricated photodissociation spectrometer permits the determination of thermodynamic properties (activation energies), reaction rates, and mechanistic details of bare metal cation mediated σ -bond activation in the gas phase. Specifically, the products and rates resulting from the unimolecular decomposition of the Ni^+Acetaldehyde adduct are monitored after absorption of a known amount of energy. The two dissociative products which are observed in high yield are Ni^+ and Ni^+CO. The Ni^+CO fragment ion could result from the activation of a C-C σ-bond or from the activation of a C-H σ-bond. The rate constant for the decarbonylation of Ni^+Acetaldehyde was approximately 30 percent greater than that of the rate constant for the decarbonylation of Ni^+Acetone. For the decarbonylation of Ni^+Acetone, there needs to be a methide shift, whereas in the decarbonylation of Ni^+Acetaldehyde one could have C-C insertion followed by an aldhyde H-shift. The rate-limiting step of the decarbonylation process will be discussed.
Bellert Darrin J.
Castleberry Vanessa A.
Dee Jason S.
Frey Sarah E.
Laboren Ivanna E.
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