Unexpected Synthesis of Oligomeric (Dimethylsilyl)-Bridged Ferrocenes from the Desilylative Coupling of Tertiary 1,1′-Bis(dimethylsilyl)ferrocene

Abstract

The solvent-free, Pt-catalyzed desilylative coupling reaction of 1,1 0 -bis(dimethylsilyl)ferrocene (12) at elevated temperature leads to the elimination of one dimethylsilane unit and the concomitant oligomerization of ferrocenes with a single dimethylsilyl bridge in low to moderate yields. Airand moisture-stable oils of the dimer (13) and trimer (14) species possessing dimethylsilyl bridges and terminal dimethylsilane end groups have been isolated by preparative TLC and characterized by HR-MS, elemental analysis, and NMR spectroscopy.Polymetallocenes comprised of a repeat unit of ferrocene and a single heteroatom (e.

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

“…The solvent‐free Karstedt's catalyst‐mediated dehydrogenation coupling of 1,1′‐bis‐(dimethylsilyl)ferrocene at 100 °C yielded oligo(ferrocenylsilane)s ( 45 and 46 ) that had a single‐silane spacer (Figure ) . A switch to a polar solvent, DMF and DMSO, afforded siloxane‐bridged polyferrocenyldisiloxane ( 47 ) and disiloxane‐bridged [3]ferrocenophane ( 48 ), respectively .…”

“…The solvent-free Karstedt's catalystmediated dehydrogenation coupling of 1,1 ′ -bis-(dimethylsilyl)ferrocene at 100 °C yielded oligo(ferrocenylsilane) s ( 45 and 46 ) that had a single-silane spacer ( Figure 11 ). [ 103 ] A switch to a polar solvent, DMF and DMSO, afforded siloxane-bridged polyferrocenyldisiloxane ( 47 ) and disiloxane-bridged [3]ferrocenophane ( 48 ), respectively. [ 104 ] The presence of the disiloxane spacer signifi cantly reduced the T g (−28 ± 3 °C) of the polyferroceneyldisiloxane ( 47 ) [ 104 ] compare to the T g (33 °C) of a previously reported polyferrocenylsilane.…”

“…[ 86 ] The T g s of this series of polymers decreased as the size of the substituent on the Cp rings increased; indeed, polymer 58 , without a substituent, featured a T m ( Table 2 ) and was crystalline, as suggested from powder X-ray diffraction Figure 11. Structures of silane-( 45 and 46 ) [ 103 ] and siloxane-bridged ( 47 ) [ 104 ] oligo(ferrocene)s. Measured in a THF solution containing about 1 × 10 −3 M of the monomer unit and 0.1 M of [( n -Bu) 4 N]PF 6 . Sweep rate = 50 mV s −1 .…”

Synthesis and Properties of Poly(ferrocenylsilane)s Containing Si-Vinylene Units in the Main Chain

“…Poly(ferrocene) is one of the most synthesized and studied metallocene containing polymers due to their characteristic features derived from the ferrocene units in the polymer. The main chain type poly(ferrocene)s have been synthesized by ring opening polymerization, condensation polymerization, coupling reaction, and so on (for examples Bellas & Rehahn, 2007;Miles, Ward, & Foucher, 2009;Miles, Ward, & Foucher, 2010;Wang, Huo, Ding, & Tan, 2008;Huo, Wang, Yu, Deng, Zhou, & Yang, 2007;Cazacu, Munteanu, Racles, Vlad, & Marcu, 2006;Caracu, Vlad, Marcu, Racles, Airinei, & Munteanu, 2006;Southard & Curti, 2001). Poly(ferrocenylsilane)s have been widely synthesized by ring opening polymerization of Si bridged ferrocene compounds, as shown in Scheme 1 (for example Bellas & Rehahn, 2007).…”

Synthesis and characterization of a polyferrocenyldistannane

“…12,13,[15][16][17] Earlier work from our group 18 described the non-ROP preparation of oligoferrocenylsilanes [Fe( 5 -C 5 H 4 ) 2 SiMe 2 ] n (n = 2-7) through a desilylative coupling of Fe( 5 -C 5 H 4 SiMe 2 H) 2 using Karstedt's catalyst in DCM. The isolation of polyferrocenyldisiloxane 2, [Fe( 5 -C 5 H 4 SiMe 2 ) 2 O] n , from Fe( 5 -C 5 H 4 SiMe 2 H) 2 using Karstedt's catalyst in DMF was also identifed.…”