No abstract

The novel complex cis-[(ITMe)2Pd(SiMe3)2 (ITMe=1,3,4,5-tetramethylimidazol-2-ylidene) has been synthesized by mild oxidative cleavage of Me3SiSiMe3 using [(ITMe)2Pd0]. The use of this complex as precatalyst for the cis-bis(silyl)ation of alkynes using unactivated disilanes is reported.

Pd(ITMe) 2 (PhCCPh) acts as a highly reactive precatalyst in the silaboration of terminal and internal alkynes to yield a number of known and novel 1-silyl-2-boryl alkenes. Unprecedented mild reaction temperatures for terminal alkynes, short reaction times, and low catalytic loadings are reported. During mechanistic studies, cis-Pd(ITMe) 2 (SiMe 2 Ph)(Bpin) was directly synthesized by oxidative addition of PhMe 2 SiBpin to Pd-(ITMe) 2 (PhCCPh). This represents a very rare example of a (silyl)(boryl)palladium complex. A plausible catalyst decomposition route was also examined.

Pd(ITMe)2(PhCCPh) is a pre-catalyst in the unprecedented homogenous catalyzed diboration of terminal and internal alkynes.