A Stable Two-Coordinate Acyclic Silylene

• Published in: Journal of the American Chemical Society Vol. 134; no. 15; pp. 6500 - 6503
• Main Authors: Protchenko, Andrey V., Birjkumar, Krishna Hassomal, Dange, Deepak, Schwarz, Andrew D., Vidovic, Dragoslav, Jones, Cameron, Kaltsoyannis, Nikolas, Mountford, Philip, Aldridge, Simon
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 18-04-2012
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja301042u

Simple two-coordinate acyclic silylenes, SiR2, have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)2 substituent (Dipp = 2,6- i Pr2C6H3), an isolable monomeric species, Si{B(NDippCH)2}{N(SiMe3)Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C–H bonds, consistent with a low singlet–triplet gap (103.9 kJ mol–1), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.