دورية أكاديمية
Spin-Crossing in the ( Z )‑Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo 3 S 4 Clusters: A Density Functional Theory Exploration
| العنوان: | Spin-Crossing in the ( Z )‑Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo 3 S 4 Clusters: A Density Functional Theory Exploration |
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| المؤلفون: | María Gutiérrez-Blanco, Andrés G. Algarra, Eva Guillamón, M. Jesús Fernández-Trujillo, Mónica Oliva, Manuel G. Basallote, Rosa Llusar, Vicent S. Safont |
| سنة النشر: | 2024 |
| مصطلحات موضوعية: | Biophysics, Biochemistry, Evolutionary Biology, Computational Biology, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, system evolve via, large energy required, internal alkynes catalyzed, computational studies indicate, – h groups, excellent selectivity toward, cluster selectively affords, 4 , 3 , 2 , stable imidazolyl amino, second alternative pathway, mild reaction conditions, first hat occurs, experimental results suggest, bridging sulfur atoms, experimental results, z <, subsequent h, soft conditions, selectively render, second hat, reaction begins |
| الوصف: | Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo 3 S 4 Cl 3 (ImNH 2 ) 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 CD 3 OD and CH 3 OD. An alternative mechanism that explains the experimental results is proposed. The reaction begins with the hydrogenation of two of the Mo 3 (μ 3 -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 H 2 addition makes the system evolve via the second alternative pathway to selectively render the ( Z )-alkene with a lower overall activation barrier. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | unknown |
| العلاقة: | https://figshare.com/articles/journal_contribution/Spin-Crossing_in_the_i_Z_i_Selective_Alkyne_Semihydrogenation_Mechanism_Catalyzed_by_Mo_sub_3_sub_S_sub_4_sub_Clusters_A_Density_Functional_Theory_Exploration/24941549Test |
| DOI: | 10.1021/acs.inorgchem.3c03057.s001 |
| الإتاحة: | https://doi.org/10.1021/acs.inorgchem.3c03057.s001Test https://figshare.com/articles/journal_contribution/Spin-Crossing_in_the_i_Z_i_Selective_Alkyne_Semihydrogenation_Mechanism_Catalyzed_by_Mo_sub_3_sub_S_sub_4_sub_Clusters_A_Density_Functional_Theory_Exploration/24941549Test |
| حقوق: | CC BY-NC 4.0 |
| رقم الانضمام: | edsbas.DC2AAD2 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acs.inorgchem.3c03057.s001 |
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