Synthesis of -Mono(silyl)palladium(II) Bromide Complexes.

The stoichiometric reaction of -[Pd(ITMe)(SiR)], where (SiR = SiMe and SiMePh and ITMe = 1,3,4,5-tetramethylimidazol-2-ylidene) with allyl bromide affords the corresponding allylsilanes along with complexes of the type -[Pd(ITMe)(SiR)(Br)]. The structure of -[Pd(ITMe)(SiMePh)Br] has been determined in the solid state and displays a slightly distorted square-planar geometry with the two N-heterocyclic carbene ligands in a -configuration.

Synthesis of Functionalized Hydrazines: Facile Homogeneous (N-Heterocyclic Carbene)-Palladium(0)-Catalyzed Diboration and Silaboration of Azobenzenes.

The bis(N-heterocyclic carbene)(diphenylacetylene)palladium complex [Pd(ITMe)(PhC≡CPh)] (ITMe=1,3,4,5-tetramethylimidazol-2-ylidene) acts as a highly active pre-catalyst in the diboration and silaboration of azobenzenes to synthesize a series of novel functionalized hydrazines. The reactions proceed using commercially available diboranes and silaboranes under mild reaction conditions.

Synthesis of an [(NHC)2 Pd(SiMe3 )2 ] Complex and Catalytic cis-Bis(silyl)ations of Alkynes with Unactivated Disilanes.

The novel complex cis-[(ITMe)2 Pd(SiMe3 )2 (ITMe=1,3,4,5-tetramethylimidazol-2-ylidene) has been synthesized by mild oxidative cleavage of Me3 SiSiMe3 using [(ITMe)2 Pd(0) ]. The use of this complex as precatalyst for the cis-bis(silyl)ation of alkynes using unactivated disilanes is reported.