Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers: Fid-Bau Portal

Fachinformationsdienst BAUdigital

Eine Plattform für die Wissenschaft: Bauingenieurwesen, Architektur und Urbanistik

Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers

Cai, Yuanting / Hua, Yuhui / Lu, Zhengyu / Chen, Jiangxi / Chen, Dafa / Xia, Haiping

Metallacyclobutadienes (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.

Zugriff

Seitennavigation

Dokumentinformationen

Ähnliche Titel

Exportieren, teilen und zitieren

Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers

Cai, Yuanting / Hua, Yuhui / Lu, Zhengyu / Chen, Jiangxi / Chen, Dafa / Xia, Haiping

Metallacyclobutadienes (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

Cai, Yuanting / Hua, Yuhui / Lu, Zhengyu / Chen, Jiangxi / Chen, Dafa / Xia, Haiping

Metallacyclobutadienes (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.

Zugriff

Seitennavigation

Dokumentinformationen

Ähnliche Titel

Exportieren, teilen und zitieren

Dokumentinformationen

Titel:

Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers

Beteiligte:

Cai, Yuanting (Autor:in) / Hua, Yuhui (Autor:in) / Lu, Zhengyu (Autor:in) / Chen, Jiangxi (Autor:in) / Chen, Dafa (Autor:in) / Xia, Haiping (Autor:in)

Erschienen in:

Advanced Science ; 11

Erscheinungsdatum:

01.10.2024

Format / Umfang:

6 pages

ISSN:

DOI:

https://doi.org/10.1002/advs.202403940

Medientyp:

Aufsatz (Zeitschrift)

Format:

Elektronische Ressource

Sprache:

Englisch

Schlagwörter:

intramolecular rearrangement , kinetic isomer , metallacyclobutadiene , metallatetrahedrane , thermodynamic isomer

Ähnliche Titel

Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers

Cai, Yuanting / Hua, Yuhui / Lu, Zhengyu et al. | Wiley | 2024

Freier Zugriff

Polymorph selection and nanocrystallite rearrangement of calcium carbonate in carboxymethyl chitosan aqueous solution: Thermodynamic and kinetic analysis

Zhao, D. / Zhu, Y. / Li, F. et al. | British Library Online Contents | 2010

Theoretical basis of 2,4-methyl migration, an intramolecular rearrangement, during isomerization of alkyladamantyl cations

Bagrii, E. I. / Borisov, Yu. A. | Springer Verlag | 2017

Relative thermodynamic stability of three-dimensional isomers of dimethylcycloheptanes and dimethylcyclo-octanes

Makushina, V.M. / Aref'ev, O.A. / Petrov, Al.A. | Elsevier | 1971

High-speed thermodynamic calculations for kinetic simulations

Strandlund, H. | British Library Online Contents | 2004