Synthesis of a Stable N-Hetero-RhI-Metallacyclic Silanone |
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| Authors: | Shintaro Takahashi Kazuki Nakaya Dr. María Frutos Dr. Antoine Baceiredo Dr. Nathalie Saffon-Merceron Dr. Stéphane Massou Dr. Norio Nakata Dr. Daisuke Hashizume Prof. Vicenç Branchadell Dr. Tsuyoshi Kato |
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| Affiliation: | 1. Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, 338-8570 Japan;2. Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France;3. Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France;4. RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan;5. Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain |
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| Abstract: | A novel N-hetero-RhI-metallacyclic silanone 2 has been synthesized. The silanone 2 , showing an extremely large dimerization energy (ΔG=+86.2 kcal mol−1), displays considerable stability and persists in solution up to 60 °C. Above 120 °C, an intramolecular Csp3−H insertion occurs slowly over a period of two weeks leading to the bicyclic silanol 5 . The exceptional stability of 2 , related to the unusual electronic and steric effects of RhI-substituent, should allow for a more profound study and understanding of these new species. Furthermore, the metallacyclic silanone 2 presents two reactive centers (Si=O and Rh), which can be involved depending upon the nature of reagents. Of particular interest, the reaction with H2 starts with the hydrogenation of RhI center leading to the corresponding RhIII-dihydride complex 7 and it undergoes a cis/trans-isomerization via a particular mechanism, demonstrating that addition-elimination processes can also happen for silanones just like for their carbon analogues! |
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| Keywords: | metallacycles NHSi rhodium complex stable silanone stable silylene |
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