Regiospecific Hydroxylation of Metallodisilanes of the Iron Group – An Impressive Example of the Transition Metal Effect

Abstract

Reaction of the ferriodisilanes C5R5(OC)2Fe–Si2H5 [R = H (1a), Me (1b)] with dimethyldioxirane leads to selective insertion of oxygen into the α‐Si–H bonds to yield the ferriodihydroxydisilanes C5R5(OC)2Fe–Si(OH)2–SiH3[R = H (2a), Me (2b)]. Another access to yield 2a is opened by hydrolysis of the dichloro(ferrio)disilane Cp(OC)2Fe–SiCl2–SiH3 (3a). Treatment of the pentachloro(metallo)disilanes C5H5(OC)2Fe–Si2Cl5 (4a) and C5Me5(OC)2Ru–Si2Cl5 (4b) with water results in regiospecific hydroxylation of the β‐silicon atom to generate metallodisilanetriols C5R5(OC)2M–SiCl2–Si(OH)3 [M = Fe, R = H (5a); M = Ru, R = Me (5b)]. Controlled condensation of 5b with Me2Si(H)Cl leads to the novel rutheniosiloxane C5Me5(OC)2Ru–SiCl2–Si(OSiMe2H)3 (6).