Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration
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Other documents of the author: Gutiérrez-Blanco, María; Algarra, Andrés G.; Guillamón, Eva; Fernández-Trujillo, M. Jesús; Oliva, Mónica; García Basallote, Manuel; Llusar, Rosa; Safont Villarreal, Vicent Sixte
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comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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INVESTIGACIONMetadata
Title
Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory ExplorationAuthor (s)
Date
2024-01-04Publisher
American Chemical SocietyISSN
0020-1669Bibliographic citation
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.3c03057Type
info:eu-repo/semantics/articlePublisher version
https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.3c03057Version
info:eu-repo/semantics/publishedVersionSubject
Abstract
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. [-]
Is part of
Inorganic Chemistry 2024 63 (2)Funder Name
Serveis Centrals d’Instrumentació Científica | Ministerio de Ciencia e Innovación | Ministerio de Economía y Competitividad | Generalitat Valenciana | Universitat Jaume I
Project code
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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