Recombination Of An Fe-si-p Linkage To An Fe-p-si Linkage Through An Isolable Intermediate Phosphasilaferracyclopropane

摘要

Silyl(silylene) complexes have attracted considerable interest as key intermediates in the metal-catalyzed oligomerization/deoligo-merization and redistribution of organosilicon compounds. Both Pannell's group and we have shown, through the generation of silyl(silylene) complexes and synthesis of their base-stabilized forms, that 1,2- and 1,3-group migration reactions of these systems occur fairly easily under mild conditions. In a study of the reactions of an isolable base-free silyl(silylene)iron complex, we recently proved that these migration reactions proceed through silyl(silylene) complexes. In the migration process, the low-lying p-orbital on the silylene silicon atom plays a crucial role, providing a low activation barrier. We report here extremely facile 1,2- and 1,3-group migrations in an FeSiP system, in which readily accessible empty p-orbitals on the silylene and phosphinidene ligands are thought to play a crucial role (Scheme 1).