A base-stabilized 2-silaallene

Abstract

The reaction of [CH2(PPh2S)2] (1) with 2 equiv of MeLi in Et2O followed by addition of 0.5 equiv of SiCl4 afforded the base-stabilized 2-silaallene [(PPh2S)2CSiC(PPh2S)2] (2). It has been characterized by X-ray crystallography, NMR spectroscopy, and theoretical studies. The results show that compound 2 comprises a C¯–Si2+–C¯ ylidic skeleton with a negative charge at the Cmethanediide atoms and two positive charges at the Si atom. The reaction of 2 with excess PriN═C═NPri in refluxing toluene gave the thiophosphinoyl-stabilized silene [(PPh2S)2C–—Si+(NPri)2C═C(PPh2S)2] (3).