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

Abstract

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)2Cp]2 [R = Me (1a), pTol (1b)] with dimethyldioxirane (2) yields the μ‐(hydroxysilanediyl)bisiron complexes [μ‐(R)(HO)Si][Fe(CO)2Cp]2 [R = Me (3a), pTol (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)2Fe‐Me (4) with MesSiH3, (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.

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…Malisch and coworkers prepared [141] a bisFp-substituted silane (Scheme 84) to use as a precursor for oxygenation with dimethyldioxirane. The subsequent bisFp-substituted silanol complex was produced in 95% yield.…”

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

“…Table − summarizes the products isolated from reactions of primary silanes, RSiH 3 , with transition-metal complexes. Most investigations with primary silanes involve R = aryl, since the low molecular weight alkyl compounds (R = Me, Et, Pr) are gases at 25 °C and thus require more specialized handling.…”

“…Si(Fe,Ru,Os) bonds prepared by other methods or preceding 1980 and structurally characterized. SiFe: 2.218(2); 2.222(3); , 2.224(1); 2.2277(14); 2.230(2); 2.2330(14); 2.249(1); , 2.249(3); 2.252(3); 2.258(1); 2.260(6); 2.262(2); , 2.262(1); 2.263(1); 2.263(2), 2.264(2); 2.264(2); 2.265(1); 2.266(3); 2.267(1); 2.268(8); 2.271(4); 2.275(2); 2.278(1); 2.280(3); 2.281(4); 2.285(3); 2.286(5); 2.286(1); 2.287(2); 2.290(3); 2.294(1); 2.296(2); 2.297(3); 2.301(1); 2.303(1); 2.307(1); 2.307(2); 2.310(1); 2.322(1); 2.311(2); 2.311(3); 2.3l3(6); 2.315(2); 2.316(13); 2.322(4); 2.325(3); 2.326(3); 2.327(3); 2.328(1); 2.33(1); 2.330(2); 2.338(4); 2.339(2); 2.339(1); 2.341(2); 2.346; 2.347(1); 2.350(1); 2.354(2); 2.356; 2.356(1); 2.357(3); , 2.364(5); 2.365(2); 2.366(2); 2.366(1); 2.375(2); 2.378(1);…”

Si−H-Functionalized Ferriodisiloxanes: Synthesis from the Ferriodimethylsilanols C5R5(OC)2Fe−SiMe2OH (R = H, Me) and Photoinduced Transformation into µ2-Disiloxanediyl-Bridged Dinuclear Iron Complexes

“…[16,20] Hydrolysis of the chloroferriodimethylsilanes 1a and 1b in diethyl ether in the presence of the auxiliary base Et 3 N at room temperature afforded the metallated silanols 2a and 2b in good yields [89% (2a), 70% (2b)] [Equation (1), route a]. The C 5 Me 5 -substituted complex 1b undergoes ligand exchange (48 h) significantly more slowly than the Cp compound 1a.…”