Reactions of Si–Si σ-Bonds with Bis(t-alkyl isocyanide)palladium(0) Complexes. Synthesis and Reactions of Cyclic Bis(organosilyl)palladium Complexes

Four- to seven-membered cyclic bis(organosilyl)palladium(II) complexes were synthesized by oxidative addition of cyclic disilanes onto bis(t-butyl isocyanide)palladium(0) as well as by intramolecular metathesis of the two Si–Si bonds of bis(disilane)s with the palladium(0) complex. The 4-membered bis(organosilyl)bis(t-butyl isocyanide)palladium complex prepared from 2,2-bis(1,1,2,2-tetramethyl-2-phenyldisilanyl)-1,3-dithiane was characterized by a single-crystal X-ray method, which showed an unusually short cross-ring Si–Si distance in the 4-membered ring. The reactivities of the cyclic bis(organosilyl)bis(t-butyl isocyanide)palladium complexes toward phosphines, cyclic disilanes, and alkynes were also examined. Cyclic organosilicon compounds were synthesized by bis-silylation of alkynes with cyclic bis(organosilyl)palladium intermediates generated by the intramolecular metathesis. The bis-silylation was also applicable for electron-deficient alkenes: α,β-unsaturated ketones gave 7-membered 1,4-bis-silylation adducts, whereas the corresponding ester and nitrile gave 5-membered 1,2-adducts in high yields.