Gas-phase reactions of La{sup 2+} with small alkanes and the photodissociation of LaC{sub 2}H{sub 4}{sup n+} and LaC{sub 3}H{sub 6}{sup n+} (n = 1 and 2)
- Purdue Univ., West Lafayette, IN (United States)
The gas-phase reactivity of La{sup 2+} with C{sub 1}-C{sub 4} linear alkanes is investigated and compared to the analogous reactions of La{sup +}. La{sup 2+} is unreactive with methane and ethane but reacts with propane and butane to give dehydrogenation, alkane loss, and for butane charge-splitting reaction products. Interestingly, charge transfer is not observed in agreement with a simple curve-crossing model. Four ligated species, namely, LaC{sub 2}H{sub 4}{sup +}, LaC{sub 2}H{sub 4}{sup 2+}, LaC{sub 3}H{sub 6}{sup +}, and LaC{sub 3}H{sub 6}{sup 2+}, are photodissociated and the photodissociation thresholds are used directly, or together with information from ligand displacement reactions, to assign thermochemical values for these processes and metal ligand bond energies. The bonding properties of LaC{sub 2}H{sub 2}{sup +} and LaC{sub 2}H{sub 2}{sup 2+} are also investigated. A surprising outcome of this study is that the monocation is in some cases more strongly bound to these ligands than the dication. Theoretical calculations by Bauschlicher and co-workers are in good agreement with these results. 28 refs., 6 figs., 5 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-87ER13766
- OSTI ID:
- 569225
- Journal Information:
- Journal of the American Chemical Society, Vol. 114, Issue 23; Other Information: PBD: 4 Nov 1992
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
LANTHANUM COMPOUNDS
GAS ANALYSIS
PHASE TRANSFORMATIONS
CARRIER MOBILITY
ELECTRON TRANSFER
DEHYDROGENATION
CHEMICAL BONDS
ACTIVATION ENERGY
CHEMICAL ACTIVATION
DISSOCIATION
ALKANES
LIGANDS
BINDING ENERGY
CHEMICAL REACTIONS
CHEMICAL REACTION KINETICS
DISSOCIATION ENERGY
CARBON
BUTANE
ETHANE
METHANE
PROPANE