Ab Initio and DFT Study of Homolytic Substitution Reactions of Acyl Radicals at Silicon, Germanium, and Tin
| Autor: | Carl H. Schiesser, Sonia M. Horvat |
|---|---|
| Rok vydání: | 2009 |
| Předmět: |
Substitution reaction
Dimethylsilane Organic Chemistry Ab initio chemistry.chemical_element Germanium Homolysis Inorganic Chemistry chemistry.chemical_compound chemistry Computational chemistry Ab initio quantum chemistry methods Nucleophilic substitution Physical chemistry Physical and Theoretical Chemistry Tin |
| Zdroj: | Organometallics. 28:3311-3318 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om801016x |
| Popis: | Ab initio calculations using the 6-311G(d,p), cc-pVDZ, aug-cc-pVDZ, and (valence) double-ζ pseudopotential (DZP) basis sets, with (MP2, ROMP2, QCISD, CCSD(T)) and without (HF) the inclusion of electron correlation, and density functional (BHandHLYP) calculations predict that homolytic substitution reactions of acetyl radicals at the silicon atoms in dimethylsilane can proceed via both backside and frontside attack mechanisms. At the highest level of theory (CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ), energy barriers (ΔE⧧) of 110.4 and 107.5 kJ mol−1 are calculated for the backside and frontside reactions, respectively. Similar results are obtained for reactions involving germanium and tin with energy barriers (ΔE⧧) of 97.6−191.7 and 100.8−171.3 kJ mol−1 for the backside and frontside mechanisms, respectively. These data suggest that both homolytic substitution mechanisms are feasible for homolytic reactions of acetyl radicals at silicon, germanium, and tin. BHandHLYP calculations provide geometries and energy ... |
| Databáze: | OpenAIRE |
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