Synthesis of a Bis(silanolate) Complex from a Bis(silyl) Complex by Air Oxidation: Evidence for the Participation of Silanolate Complexes in the Transition-Metal-Catalyzed Formation of Disiloxanes from Hydridosilanes

In a novel type of reaction, the bis(silyl) complex (κ 2 - P, N )-(PN)Pt[ o -(Me 2 Si) 2 C 6 H 4 ] (PN = 2-(diphenylphosphino)- N, N -dimethylaniline) was quantitatively converted to the bis(silanolate) analogue (κ 2 - P, N )-(PN)Pt[ o -(OMe 2 Si) 2 C 6 H 4 ]. Reaction of the bis(silanolate) complex with 1,2-bis(dimethylsilyl)benzene under argon leads to the starting bis(silyl) complex along with 1,1,3,3-tetramethyl-4,5-benzo-2-oxa-1,3-disilacyclopent-4-ene. In air the bis(silane) is quantitatively converted to the siloxane by catalytic amounts of the bis(silanolate) complex.