Synthesis of a Stable N‐Hetero‐Rh^I‐Metallacyclic Silanone

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!

Strained and Reactive Donor/Acceptor‐Supported Metallasilanone

“…[6] Even though some recent studies have demonstrated that bulky or/and strongly s-or/and p-donating substituents efficiently stabilize silanones, the synthesis of stable silanones I remains a great challenge and, to date, only a limited number of isolable silanones are available. [7][8][9][10][11][12] A drastic improvement in the stability was achieved by Driesss group, using donor (II) [13] or donor/acceptor (III) [14] systems. [15][16][17][18][19] Thanks to that, several stable and easy-tomanipulate silanone derivatives have been prepared.…”