Abstract Difluorocarbene, CF 2, generated by thermal decomposition of Cf 3 SiF 3 at 100 C, has been found to insert into the Si H bonds of halosilanes SiH 3 X (X= F, Cl, Br, I), methylhalosilanes CH 3 SiH 2 X (X= Br, Cl) and (CH 3) 2 SiHCl, and disiloxane (SiH 3) 2 O. Use of excess of the CF 2-source CF 3 SiF 3 and of pressure favour the formation of the di- insertion products (CHF 2) 2 SiHX and (CHF 2) 2 (CH 3) SiX.(CHF 2) 3 SiCl was identified ...