1,1′-Bis(stannyl)- and 1,1′-Bis(chlorostannyl)ferrocenes Studied by Multinuclear Magnetic Resonance, Temperature-Dependent57Fe- and119Sn-Mössbauer Spectroscopy, and Electrochemistry

Abstract

The 1,1′‐bis(chlorostannyl)‐substituted ferrocenes Fe(C5H4–SnMe2Cl)2 (2), Fe(C5H4–SnMeCl2)2 (3) and Fe(C5H4–SnCl3)2 (4) were prepared, starting from 1,1′‐bis(trimethylstannyl)ferrocene (1). Treatment of the chlorides with Li[AlH4] afforded the 1,1′‐bis(hydridostannyl)‐subsituted ferrocenes Fe(C5H4–SnMe2H)2 (5), Fe(C5H4–SnMeH2)2 (6) and Fe(C5H4‐SnH3)2 (7), respectively. All complexes 1–7 were studied by 1H‐, 13C‐, and 119Sn‐NMR spectroscopy with 1D and 2D techniques. The compounds 1–4 were investigated by temperature‐dependent 119Sn‐ and 57Fe‐Mössbauer spectroscopy. The electrochemistry of 1–5 gave evidence of reversible one‐electron oxidation processes. The molecular structure of 1,1′‐bis(trichlorostannyl)ferrocene (4) was determined by X‐ray structural analysis, and there was no indication of intra‐ or intermolecular Sn···Cl···Sn interactions. This direct structural information proved to be consistent with both the Mössbauer and the solution NMR spectroscopic data.

[{Fe(C5H4)2}3{Ga(C5H5N)}2]: A Trinuclear Gallium-Bridged Ferrocenophane with a Carousel Structure

“…The complex 1,1′‐bis(dimethylgallyl)ferrocene4 ( 2 ), reported here for the first time, is prepared in good yield from 1,1′‐bis(trichlorostannyl)ferrocene ( 1 )5 with an excess of trimethylgallium (Scheme ) and serves as the starting material. This orange compound, which is sparingly soluble in nondonating solvents and extremely air sensitive, is presumably a coordination polymer made up of [{Fe(C 5 H 4 )( μ 2 ‐GaMe 2 ) 2 (C 5 H 4 )} n ] units with bridging GaMe 2 units which form four‐membered Ga 2 C 2 rings (for comparison: dimethylgallylferrocene has a dimeric structure with GaMe 2 bridges6).…”

[{Fe(C5H4)2}3{Ga(C5H5N)}2] - ein dreikerniges galliumverbrücktes Ferrocenophan mit Karussellstruktur

“…Als Ausgangsverbindung dient das hier erstmals beschriebene 1,1′‐Bis(dimethylgallyl)ferrocen4 2 , welches man in guter Ausbeute durch Umsetzung von 1,1′‐Bis(trichlorstannyl)ferrocen 1 5 mit einem Überschuss Trimethylgallium erhält (Schema ). Die orangefarbene, in donorfreien Solventien schwerlösliche sowie extrem luftempfindliche Verbindung liegt vermutlich als aus [{Fe(C 5 H 4 )( μ 2 ‐GaMe 2 ) 2 (C 5 H 4 )} n ]‐Einheiten gebildetes Koordinationspolymer mit verbrückenden und Ga 2 C 2 ‐Vierringe bildenden GaMe 2 ‐Einheiten vor (zum Vergleich: Dimethylgallylferrocen hat eine dimere Struktur mit GaMe 2 ‐Brücken6).…”

Synthesis and characterization of ferrocenyl stannanes and polyferrocenyl stannanes

“…Dodo et al 103 were able to produce a series (Et, n-Pr, n-Bu) of (η system lead to production of a series of disubstituted mono-, di-and tri-chlorides, as well as the corresponding hydrides (Figure 1.13). 106 A variety of interesting structural ferrocenyl stannanes have produced through the systems described. Lenze et al was able to prepare a series of multi-substituted methylstannylferrocenes through reactions with mono-and dilithioferrocene as well as through the initial formation of substituted cyclopentadiene rings that were then further reacted with FeCl 2 to form the corresponding ferrocene analogue.…”

“…With the addition of chlorine to the Sn center, the 119 Sn chemical resonances moved down field to 126.8 ppm, similar to values reported by Herberhold. 106 Both 1a and 3a…”

“…The intermediate, 2a, was reacted further without purification and identified only by 119 Sn NMR spectroscopy (δ = 126.8 ppm, CDCl 3 ), in good agreement with reported literature values. 106 Approximately 150 mL of Et 2 O was added to the previous reaction mixture. 58…”