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Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers
https://orcid.org/0000-0002-7650-4024
https://orcid.org/0000-0002-2688-6634
AbstractMetallacyclobutadienes (MCBDs) are key intermediates of alkyne metathesis reactions. There are in principle two isomerization pathway from kinetic to thermodynamic MCBDs, intermolecular and intramolecular. However, systems that simultaneously isolate two kinds of MCBD isomers have not been achieved, thus restricting the mechanistic studies of the isomerization. Here the reactivity of a metallapentalyne that contains an M≡C bond within the aromatic ring, with alkynes to afford a series of MCBD‐fused metallapentalenes is studied. In some cases, both kinetic and thermodynamic products are isolated in the same system, which has never been observed in previous MCBD reactions. Furthermore, the isomerization of MCBD‐fused metallapentalenes is investigated both experimentally and theoretically, indicating that it is an intramolecular process involving a metallatetrahedrane (MTd) intermediate. This research provides experimental evidence demonstrating that one MCBD can undergo intramolecular rearrangement to transform into another.
Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers
https://orcid.org/0000-0002-7650-4024
https://orcid.org/0000-0002-2688-6634
AbstractMetallacyclobutadienes (MCBDs) are key intermediates of alkyne metathesis reactions. There are in principle two isomerization pathway from kinetic to thermodynamic MCBDs, intermolecular and intramolecular. However, systems that simultaneously isolate two kinds of MCBD isomers have not been achieved, thus restricting the mechanistic studies of the isomerization. Here the reactivity of a metallapentalyne that contains an M≡C bond within the aromatic ring, with alkynes to afford a series of MCBD‐fused metallapentalenes is studied. In some cases, both kinetic and thermodynamic products are isolated in the same system, which has never been observed in previous MCBD reactions. Furthermore, the isomerization of MCBD‐fused metallapentalenes is investigated both experimentally and theoretically, indicating that it is an intramolecular process involving a metallatetrahedrane (MTd) intermediate. This research provides experimental evidence demonstrating that one MCBD can undergo intramolecular rearrangement to transform into another.
Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers
https://orcid.org/0000-0002-7650-4024
https://orcid.org/0000-0002-2688-6634
AbstractMetallacyclobutadienes (MCBDs) are key intermediates of alkyne metathesis reactions. There are in principle two isomerization pathway from kinetic to thermodynamic MCBDs, intermolecular and intramolecular. However, systems that simultaneously isolate two kinds of MCBD isomers have not been achieved, thus restricting the mechanistic studies of the isomerization. Here the reactivity of a metallapentalyne that contains an M≡C bond within the aromatic ring, with alkynes to afford a series of MCBD‐fused metallapentalenes is studied. In some cases, both kinetic and thermodynamic products are isolated in the same system, which has never been observed in previous MCBD reactions. Furthermore, the isomerization of MCBD‐fused metallapentalenes is investigated both experimentally and theoretically, indicating that it is an intramolecular process involving a metallatetrahedrane (MTd) intermediate. This research provides experimental evidence demonstrating that one MCBD can undergo intramolecular rearrangement to transform into another.
Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers
Advanced Science
Cai, Yuanting (author) / Hua, Yuhui (author) / Lu, Zhengyu (author) / Chen, Jiangxi (author) / Chen, Dafa (author) / Xia, Haiping (author)
Advanced Science ; 11
2024-10-01
Article (Journal)
Electronic Resource
English
Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers
| Wiley | 2024
| British Library Online Contents | 2010
High-speed thermodynamic calculations for kinetic simulations
| British Library Online Contents | 2004