Synthese und Reaktivität von Silicium‐Übergangsmetall‐Komplexen, 35. Metallo‐silanole und Metallo‐siloxane, 9. Synthese des diastereomerenreinen Ferrio‐silanols (RS,SR)‐Cp(OC)(Ph₃P)Fe‐Si(Me)(Ph)(OH) und Struktur von (RR,SS)‐Cp(OC)(Ph₃P)Fe‐Si(Me)(Ph)Cl

Abstract

Synthesis and Reactivity of Silicon Transition Metal Complexes, 35 . — Metallo Silanols and Metallo Siloxanes, 9 . — Synthesis of the Diastereomerically Pure Ferrio Silanol (RS,SR)‐Cp(OC)(Ph3P)Fe‐Si(Me)(Ph)(OH) and Structure of (RR,SS)‐Cp(OC)(Ph3P)Fe‐Si(Me)(Ph)Cl Irradiation of the ferrio chlorosilane Cp(OC)2Fe‐Si(Me)‐(Ph)Cl (1) in the presence of Ph3P leads to Cp(OC)(Ph3P)‐Fe‐Si(Me)(Ph)Cl (2) which is formed as a mixture of diastereomers separated by crystallization. Pure (RR,SS)‐2 is converted highly stereoselectively into (RR,SS)‐Cp(OC)(Ph3P)‐Fe‐Si(Me)(Ph)H (3) with LiAlH4, and further with dimethyldioxirane into (RS,SR)‐Cp(OC)(Ph3P)Fe‐Si(Me)(Ph)(OH) (4). This ferrio silanol diasteromer is alternatively obtained by Cl/OH exchange with KOH from 2. Diastereomerically pure (RR,SS)‐2 is characterized by a single‐crystal structure analysis.

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…The subsequent bisFp-substituted silanol complex was produced in 95% yield. In a similar manner, an Fp-substituted methylphenylchlorosilane complex was prepared [142] (Scheme 84) as a precursor to its corresponding triph- Scheme 83. enylphosphine hydrosilane then subsequently converted to a silanol via reaction with dimethyldioxirane.…”

Dioxiranes: from oxidative transformations to chemiluminescence

“…304 Ferrohydridosilanes react with 1a to give the corresponding ferrosilanols. 305,306 The reaction of the ylide (Z 6 -arene)chromiumtricarbonyl complex 55 with the dioxirane 1a gives the corresponding lactone complex, which is converted in the metal-free lactone on further addition of the oxidant. 307 The oxidative capacity of dioxiranes is clearly illustrated taken as an example the transformation of tolane manganese-containing complexes into a-oxocarbene complexes (apparently, this reaction proceeds via intermediate epoxidation of the alkyne).…”

Hydroxysilylene-Bridged Dinuclear Iron Complexes [Cp(OC)2Fe]2Si(X)OH (X = H, Cl, OH): Synthesis, Structural Characterization, and Condensation with Chlorodimethylsilane

“…Consequently, a huge number of compounds containing a metal−silicon bond have been prepared in the past decades by various synthetic methods, and special attention has been given to the effect of transition metal fragments to the reactivity of the silicon atom . Among the most outstanding findings concerning the “transition metal effect” the significant stabilization of silanols, -diols, and -triols must be pointed out, which makes them attractive precursors for the designed buildup of metallo-siloxanes, including examples with stereogenic silicon and transition metal centers, e.g., Cp(OC)(Ph 3 P)Fe−Si(Me)(Ph)OH …”