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Synthesis of a Stable N‐Hetero ‐ Rh I ‐Metallacyclic Silanone
Author(s) -
Takahashi Shintaro,
Nakaya Kazuki,
Frutos María,
Baceiredo Antoine,
SaffonMerceron Nathalie,
Massou Stéphane,
Nakata Norio,
Hashizume Daisuke,
Branchadell Vicenç,
Kato Tsuyoshi
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006088
Subject(s) - chemistry , isomerization , steric effects , intramolecular force , substituent , bicyclic molecule , rhodium , reagent , silanol , stereochemistry , medicinal chemistry , migratory insertion , catalysis , organic chemistry
A novel N‐hetero‐Rh I ‐metallacyclic silanone 2 has been synthesized. The silanone 2 , showing an extremely large dimerization energy (Δ G =+86.2 kcal mol −1 ), displays considerable stability and persists in solution up to 60 °C. Above 120 °C, an intramolecular C sp3 −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 Rh I ‐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 H 2 starts with the hydrogenation of Rh I center leading to the corresponding Rh III ‐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!