Synthesis of Self-Stabilized and Donor-Free Silyl(silylene)tungsten Complexes

Photolysis of Cp‘W(CO) 3 Me ( 1a, Cp‘ = η-C 5 Me 5; 1b, Cp‘ = η-C 5 Me 4 Et) in the presence of excess HSiMe 2 SiMe 3 afforded a self-stabilized silyl(silylene)tungsten complex with a dimeric structure, [Cp‘W(CO) 2 ( SiMe 2 )(SiMe 3 )] 2 ( 2a, Cp‘ = η-C 5 Me 5; 2b, Cp‘ = η-C 5 Me 4 Et), respectively. In contrast, photolysis of 1a in the presence of HSiMe 2 SiMeMes 2 (Mes = 2,4,6-Me 3 C 6 H 2 ) resulted in the formation of the first donor-free silyl(silylene) complex with only alkyl and aryl substituents on the silicon atoms, Cp‘W(CO) 2 ( SiMes 2 )(SiMe 3 ) ( 3 ).