Interconversion of ROC+ and RCO+ (R = H and CH3): Gas-Phase Catalysis by Argon and Dinitrogen
| Autor: | Alwin Cunje, Diethard K. Bohme, Alan C. Hopkinson |
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| Rok vydání: | 1998 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 102:478-483 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp9726549 |
| Popis: | Molecular orbital calculations using density functional theory at the B3LYP/6-311++G(d,p) level have been used to optimize structures for ions COR+···M and M···RCO+ and also for the transition structures COR+···M(ts) for their interconversion (R = H, CH3 and M = Ar and N2). For the unsolvated ions and for ions COH+···M, M···HCO+, and COH+···M(ts) the optimized structures were used for single-point calculations at QCISD(T)(full)/6-311++G(2df,p). Critical points on the COH+ and ArCOH+ potential energy surfaces were also optimized at MP2(full)/6-311++G(3df,3pd). For the uncomplexed ions COR+, the barriers to 1,2-migration of R+ at B3LYP/6-311++G(d,p) are 35.4 kcal mol-1 for R = H and 14.2 kcal mol-1 for R = CH3. Inclusion of a dinitrogen molecule removes this barrier by permitting COR+ to deposit R+ on N2 followed by CO retrieving the R+ to produce the lower energy isomer, RCO+. Argon has a lower R+ affinity than the oxygen atom of CO and does not remove R+ from COR+. Preferential stabilization by argon of t... |
| Databáze: | OpenAIRE |
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