KINETIC AND THERMODYNAMIC STUDIES OF GASEOUS METALLO-ORGANIC CATIONIC COMPLEXES
Creators:Dee, S. Jason
Castleberry, Vanessa A.
Villarroel, Otsmar J.
Laboren, Ivanna E.
Frey, Sarah E.
Bellert, Darrin J.
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Publisher:Ohio State University
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 $\sigma $-bond activation in the gas phase. Specifically, the products and rates resulting from the unimolecular decomposition of the Ni$^+$Acetaldehyde adduct are monitored after absorption of a known amount of energy. The two dissociative products which are observed in high yield are Ni$^+$ and Ni$^+$CO. The Ni$^+$CO fragment ion could result from the activation of a C-C $\sigma$-bond or from the activation of a C-H $\sigma$-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.
Author Institution: Department of Chemistry and Biochemistry, Baylor University, Waco, Texas, 76798
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