Electrophilic Impact of High-Oxidation State Main-Group Metal and Ligands on Alkane C–H Activation and Functionalization Reactions
| Autor: | Ashley Holdaway, Clinton R. King, Daniel H. Ess, Nick Rollins, Roy A. Periana, Michael M. Konnick |
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| Rok vydání: | 2018 |
| Předmět: |
Alkane
chemistry.chemical_classification 010405 organic chemistry Ligand Organic Chemistry 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Transition metal chemistry Main group element Oxidation state Electrophile Reactivity (chemistry) Carboxylate Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 37:3045-3054 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic alkane C–H functionalization reactions. However, there is little known about how selection of the p-block, main-group metal and ligand impact alkane C–H activation and functionalization thermodynamics and reactivity. This work reports density functional theory calculations used to determine qualitative and quantitative features of C–H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d10s0 InIII, TlIII, SnIV, and PbIV carboxylate complexes with methane. While the main-group metal influences the C–H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact on C–H activation with stabilized carboxylate anions inducing the lowest barriers. For metal-methyl reductive functionalization reactions, the main-group metal dramatically influences the barrier heights, which are correlated to reaction... |
| Databáze: | OpenAIRE |
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