Functionalized Cyclic Disilenes via Ring Expansion
of Cyclotrisilenes with Isocyanides
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Abstract
The
reaction of cyclotrisilenes <b>1</b> with 1 equiv of alkyl and
aryl isocyanides at 25 °C affords the four-membered trisilacyclobutenes <b>2</b> with an exocyclic imine functionality as the major products
of formal insertion into one of the Si–Si single bonds of <b>1</b>. Minor quantities of the iminotrisilabicyclo[1.1.0]butanes <b>3</b> are obtained as side products, formally resulting from [1
+ 2] cycloaddition of the isocyanides to the Si–Si double bond
of <b>1</b>. The bicyclo[1.1.0]butanes <b>3</b> become
dominant at lower temperatures and may react with an additional 1
equiv of isonitriles to give the diiminotrisilabicyclo[1.1.1]pentanes <b>4</b>
