Synthesis and Reactivity of Silicon‐Transition Metal Complexes, 3l . Metallosilanols and Metallosiloxanes, 6 . Die ersten Hydroxysilandiyl‐verbrückten Zweikernkomplexe: Selektive Oxygenierung der Silicium‐Brücke in Silandiyleisen‐Komplexen mit Dimethyldioxiran

Synthesis and Reactivity of Silicon‐Transition Metal Complexes, 31 — Metallosilanols and Metallosiloxanes, 6. — The First Hydroxysilanediyl‐Bridged Binuclear Complexes: Selective Oxofunctionalization of the Silicon Bridge in Silanediyliron Complexes with Dimethyldioxirane Oxygenation of [μ‐(R)(H)Si][Fe(CO) 2 Cp] 2 [R = Me ( 1a ), p Tol ( 1b )] with dimethyldioxirane ( 2 ) yields the μ‐(hydroxysilanediyl)bisiron complexes [μ‐(R)(HO)Si][Fe(CO) 2 Cp] 2 [R = Me ( 3a ), p Tol ( 3b )]. In an analogous manner the cyclic complex (μ‐OC)[μ‐(Mes)(H)Si][Fe(CO)Cp] 2 (Fe‐Fe) ( 6 ) obtained by photochemical reaction of Cp(OC) 2 Fe‐Me ( 4 ) with MesSiH 3 , ( 5 ) is converted into (μ‐OC)[μ‐(Mes)(HO)Si][Fe(CO)Cp] 2 ‐(Fe‐Fe) ( 7 ). 6 and 7 are obtained as a mixture of cis (Mes), cis (H or OH), and trans isomers.