Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration
Impacto
![Google Scholar](/xmlui/themes/Mirage2/images/uji/logo_google.png)
![Microsoft Academico](/xmlui/themes/Mirage2/images/uji/logo_microsoft.png)
Metadatos
Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONMetadatos
Título
Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory ExplorationAutoría
Fecha de publicación
2024-01-04Editor
American Chemical SocietyISSN
0020-1669Cita bibliográfica
María Gutiérrez-Blanco, Andrés G. Algarra, Eva Guillamón, M. Jesús Fernández-Trujillo, Mónica Oliva, Manuel G. Basallote, Rosa Llusar, and Vicent S. Safont. Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration. Inorganic Chemistry 2024 63 (2), 1000-1009 DOI: 10.1021/acs.inorgchem.3c03057Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.3c03057Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo3S4Cl3(ImNH2)3]+ cluster selectively affords the (Z)-alkene under soft conditions in excellent yields. Experimental results suggest ... [+]
Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo3S4Cl3(ImNH2)3]+ cluster selectively affords the (Z)-alkene under soft conditions in excellent yields. Experimental results suggest a sulfur-based mechanism with the formation of a dithiolene adduct through interaction of the alkyne with the bridging sulfur atoms. However, computational studies indicate that this mechanism is unable to explain the experimental outcome: mild reaction conditions, excellent selectivity toward the (Z)-isomer, and complete deuteration of the vinylic positions in the presence of CD3OD and CH3OD. An alternative mechanism that explains the experimental results is proposed. The reaction begins with the hydrogenation of two of the Mo3(μ3-S)(μ-S)3 bridging sulfurs to yield a bis(hydrosulfide) intermediate that performs two sequential hydrogen atom transfers (HAT) from the S–H groups to the alkyne. The first HAT occurs with a spin change from singlet to triplet. After the second HAT, the singlet state is recovered. Although the dithiolene adduct is more stable than the hydrosulfide species, the large energy required for the subsequent H2 addition makes the system evolve via the second alternative pathway to selectively render the (Z)-alkene with a lower overall activation barrier. [-]
Publicado en
Inorganic Chemistry 2024 63 (2)Entidad financiadora
Serveis Centrals d’Instrumentació Científica | Ministerio de Ciencia e Innovación | Ministerio de Economía y Competitividad | Generalitat Valenciana | Universitat Jaume I
Código del proyecto o subvención
PID2022-141089NB-I00 | PID2019-107006GB-C22 | CIAICO/2021/122 | PRE2019-088511, UJI-B2021-29, UJI-B2022-56
Derechos de acceso
© 2024 The Authors.
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
Aparece en las colecciones
- QFA_Articles [821]