Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration
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Altres documents de l'autoria: Gutiérrez-Blanco, María; Algarra, Andrés G.; Guillamón, Eva; Fernández-Trujillo, M. Jesús; Oliva, Mónica; García Basallote, Manuel; Llusar, Rosa; Safont Villarreal, Vicent Sixte
Metadades
Mostra el registre complet de l'elementcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
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Títol
Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory ExplorationAutoria
Data de publicació
2024-01-04Editor
American Chemical SocietyISSN
0020-1669Cita bibliogràfica
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.3c03057Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.3c03057Versió
info:eu-repo/semantics/publishedVersionParaules clau / Matèries
Resum
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. [-]
Publicat a
Inorganic Chemistry 2024 63 (2)Entitat finançadora
Serveis Centrals d’Instrumentació Científica | Ministerio de Ciencia e Innovación | Ministerio de Economía y Competitividad | Generalitat Valenciana | Universitat Jaume I
Codi del projecte o subvenció
PID2022-141089NB-I00 | PID2019-107006GB-C22 | CIAICO/2021/122 | PRE2019-088511, UJI-B2021-29, UJI-B2022-56
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© 2024 The Authors.
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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