The Insertion of E II and E IV Chlorides (E=Si, Ge) into the Si-Si Bond of Disilylene.

Reactions of silicon and germanium dichlorides L⋅ECl 2 (E=Si, L=IPr; E=Ge, L=dioxane) with the phosphinoamidinato-supported disilylene ({κ 2 (N,P)-NNP}Si) 2 resulted in formal tetrylene insertions into the Si-Si bond. In the case of the reaction with silylene, two products were isolated. The first product ({κ 2 (N,P)-NNP}Si) 2 SiCl 2 , is the formal product of direct SiCl 2 insertion into the Si-Si bond of ({κ 2 (N,P)-NNP}Si) 2 and thus features two separated silylamido silylene centers. Over time, migration of the SiCl 2 group to a lateral position afforded the second product, the disilylene {κ 2 (Si,P)-SiCl 2 NNP}Si-Si{κ 2 (N,P)-NNP}. In contrast, insertion of GeCl 2 resulted only in the isolation of the germanium analogue of {κ 2 (Si,P)-SiCl 2 NNP}Si-Si{κ 2 (N,P)-NNP}, containing a Ge atom in the central position namely, compound {κ 2 (Si,P)-SiCl 2 NNP}Ge-Si{κ 2 (N,P)-NNP}, which is a rare example of a silylene-germylene. Finally, reaction of disilylene ({κ 2 (N,P)-NNP}Si) 2 with SiCl 4 and SiHCl 3 led to the formation of the new bis(silyl)silylene, ({NNP}SiCl 2 ) 2 Si:. All four new products from these insertion reactions have been characterized by multinuclear NMR and single-crystal X-ray diffraction studies.