Ag2O versus Cu2O in the Catalytic Isomerization of Coordinated Diaminocarbenes to Formamidines: A Theoretical Study
| Autor: | Juan F. Van der Maelen, Javier Ruiz |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: |
organometallic compounds
DFT calculations heterogeneous catalysis computational simulations Technology Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 |
| Zdroj: | Materials, Vol 15, Iss 2, p 491 (2022) |
| Druh dokumentu: | article |
| ISSN: | 1996-1944 |
| DOI: | 10.3390/ma15020491 |
| Popis: | DFT theoretical calculations for the Ag2O-induced isomerization process of diaminocarbenes to formamidines, coordinated to Mn(I), have been carried out. The reaction mechanism found involves metalation of an N-H residue of the carbene ligand by the catalyst Ag2O and the formation of a key transition state showing a μ-η2:η2 coordination of the formamidinyl ligand between manganese and silver, which allows a translocation process of Mn(I) and silver(I) ions between the carbene carbon atom and the nitrogen atom, before the formation of the formamidine ligand is completed. Calculations carried out using Cu2O as a catalyst instead of Ag2O show a similar reaction mechanism that is thermodynamically possible, but highly unfavorable kinetically and very unlikely to be observed, which fully agrees with experimental results. |
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