Computational Mechanistic Study of Fused Phenol Formations from 1,6‐Heptadiyne Involving Carbyne Complexes
In: ChemCatChem, Jg. 13 (2021-10-05), S. 4912-4924
Online
unknown
Zugriff:
The reaction of a tungsten carbyne complex, MeC≡WBr(CO)4, with 1,6-heptadiyne was investigated using density functional theory (DFT) calculations. It was suggested that the plausible mechanism involves [2+2] cycloaddition of the carbyne with the diyne, subsequent insertion of CO and alkyne into a metallacyclobutadiene intermediate, and a final reductive elimination step from a metallacycloheptatrienone intermediate to produce a η^5-cyclohexadienyl complex. A related Ru-catalyzed reaction of 1,6-heptadiyne involving a hydroxycarbyne complex was investigated to propose a possible pathway starting from a bis(hydroxycarbyne) complex, (HOC≡)2Ru(CO)2. It was found that the biscarbyne complex undergoes carbyne-carbyne coupling to generate a stable metallacyclopropene intermediate, which reacts with 1,6-heptadiyne through two different pathways to produce the final η^6-arene complex. Moreover, a non-carbyne pathway was also investigated to propose an alternative mechanism.
Titel: |
Computational Mechanistic Study of Fused Phenol Formations from 1,6‐Heptadiyne Involving Carbyne Complexes
|
---|---|
Autor/in / Beteiligte Person: | Yamamoto, Yoshihiko |
Link: | |
Zeitschrift: | ChemCatChem, Jg. 13 (2021-10-05), S. 4912-4924 |
Veröffentlichung: | Wiley, 2021 |
Medientyp: | unknown |
ISSN: | 1867-3899 (print) ; 1867-3880 (print) |
DOI: | 10.1002/cctc.202101218 |
Schlagwort: |
|
Sonstiges: |
|