In:
Angewandte Chemie, Wiley, Vol. 132, No. 37 ( 2020-09-07), p. 16071-16075
Abstract:
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!
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v132.37
DOI:
10.1002/ange.202006088
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
505868-5
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
514305-6
detail.hit.zdb_id:
505872-7
detail.hit.zdb_id:
1479266-7
detail.hit.zdb_id:
505867-3
detail.hit.zdb_id:
506259-7
Bookmarklink