Über oligomere siliciumverbindungen mit funktionellen gruppen. 17. Mitt. Herstellung und polyadditionsreaktionen des 1,1′‐bis‐(dimethylhydrosilyl)‐ferrocens

Abstract

Durch Reduktion von 1,1′‐Bis‐(dimethyläthoxysilyl)‐ferrocen mit LiAlH4 erhielten wir in über 90% Ausbeute das 1,1′‐Bis‐(dimethylhydrosilyl)‐ferrocen (I), das sich an Acetylen zum 1,1′‐Bis‐(dimethylvinylsilyl)‐ferrocen (II) addiert: Die Polyaddition von (I) mit (II) bzw. von (I) mit anderen siliciumorganischen Verbindungen mit zwei ungesättigten Endgruppen sowie auch von (II) mit siliciumorganischen Verbindungen mit zwei H—Si‐Endgruppen ergibt thermostabile Polymere, die Ferrocenylenreste in der Hauptkette eingebaut enthalten und je nach dem Verhältnis der beiden Partner zwei H—Si‐ oder auch zwei Alkenyl‐Si‐Endgruppen tragen.

1,1‘-Bis(dimethylvinylsilyl)ferrocene as a Two-Directional Core for the Construction of Homo- and Heterometallic Systems

“…Thirty-five years ago, Greber and Hallensleben briefly described the synthesis of compound 1, which was prepared at that time by the hydrosilylation reaction of 1,1′-bis(dimethylhydrosilyl)ferrocene with acetylene in the presence of H 2 PtCl 6 as catalyst. 28 Only minimal characterization data (IR) were reported. In our laboratory, we have prepared and fully characterized this divinyl-functionalized ferrocenyl derivative 1, which has now been synthesized by reaction of Fe(η 5 -C 5 H 4 Li) 2 ‚ TMEDA (TMEDA ) N,N,N′,N′-tetramethylethylenediamine) with dimethylvinylchlorosilane in hexane at -78 °C.…”

“…These difficulties prompted us to explore the use of a different divinyl-functionalized ferrocene as the key reactive organometallic molecule, such as 1,1‘-bis(dimethylvinylsilyl)ferrocene ( 1 ) (Scheme ), in which the reactive vinyl sites are separated from the cyclopentadienyl ring and protected by the SiMe 2 group. Thirty-five years ago, Greber and Hallensleben briefly described the synthesis of compound 1 , which was prepared at that time by the hydrosilylation reaction of 1,1‘-bis(dimethylhydrosilyl)ferrocene with acetylene in the presence of H 2 PtCl 6 as catalyst . Only minimal characterization data (IR) were reported.…”

Organometallic Polymers with Transition Metals in the Main Chain

“…Greber and Hallensleben have reported the use of Diels-Alder 142 and platinum-catalyzed 142,143 polyaddition reactions of vinyl ferrocene derivatives to prepare ferrocene-containing poly(carbosilanes). These reactions were also used to prepare materials with additional functional groups leading to ferrocene and silicon-containing polyesters, polyamides, and polyurethanes.…”

Highly Selective Synthesis and Structural Characterization of Bis(silyl)-[3]-ferrocenophane Derivatives

“…Representative Procedure for Synthesis of 1,1 ‘ -Bis(vinylsilyl)ferrocene Derivatives. The title substrates were synthesized in a manner similar to that reported in ref a with modifications. For the first time, the method of synthesis of monomer 1 (Scheme ) was described forty years ago, by means of hydrosilylation reaction 17b.…”