A stable two-coordinate acyclic silylene

Andrey V Protchenko; Krishna Hassomal Birjkumar; Deepak Dange; Andrew D Schwarz; Dragoslav Vidovic; Cameron Jones; Nikolas Kaltsoyannis; Philip Mountford; Simon Aldridge

doi:10.1021/ja301042u

A stable two-coordinate acyclic silylene

J Am Chem Soc. 2012 Apr 18;134(15):6500-3. doi: 10.1021/ja301042u. Epub 2012 Apr 6.

Authors

Andrey V Protchenko¹, Krishna Hassomal Birjkumar, Deepak Dange, Andrew D Schwarz, Dragoslav Vidovic, Cameron Jones, Nikolas Kaltsoyannis, Philip Mountford, Simon Aldridge

Affiliation

¹ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.

PMID: 22443679
DOI: 10.1021/ja301042u

Abstract

Simple two-coordinate acyclic silylenes, SiR(2), 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)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))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.