Cyclic and linear poly(ferrocenylene alkylene)s synthesized from addition‐condensation polymerization of ferrocene with aldehydes

Abstract

Oligo‐ and poly(ferrocenylene alkylene)s, [Fe(C5H5‐x)(C5H5‐y)CHR]n (x = y = 1 or x = 2, y = 0; R = alkyl, aryl), were synthesized by Lewis acid‐promoted addition‐condensation polymerization of ferrocene with aldehydes. The reaction of alkyl aldehydes, such as n‐hept‐CHO, EtCHO and nBuCHO, with ferrocene yields a mixture of the cyclic and linear poly(ferrocenylene alkylene)s, while aryl aldehyde, such as C6F5CHO, CF3C6H4‐4‐CHO and MeC6H4‐4‐CHO, forms the linear polymers exclusively. The linear polymer has terminal Fe(C5H4)(C5H5) and CH2Aryl groups, which are characterized by high resolution mass spectroscopy. Results of addition‐condensation polymerization of ferrocenemethanol catalyzed by BF3 indicate that the propagating polymer of the above addition‐condensation polymerization contains terminal 1‐hydroxyalkyl‐ferrocenylene group, Fe(C5H4)[C5H4{CH(OH)R}]. The trimer prepared from ferrocene and paraformaldehyde dimethylacetal contains 1,1′‐, 1,2‐, and 1,3‐ferrocenylene units, suggesting that the polymers obtained from alkyl and aryl aldehydes are also composed of these structural units. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3627–3635

Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization

“…The new signal at δ = 29 ppm can be assigned to the formation of a bridging Fc C H 2 Fc motif. A similar NMR resonance signal for this structural motif was observed for diferrocenylmethane 53…”

Ferrocene-Based Porous Organic Polymer (FPOP): Synthesis, Characterization and an Electrochemical Study

“…The dominance of 1,1 -structure over 1,3-dialkylated and other polyalkylated ferrocenes are due to the protic acid catalyzed trans-alkylation (i.e., retro-Friedel-Crafts) reaction, which favors the formation of 1,1 -disubstituted ferrocene. As no acid was added to the reaction media, the most probable protic acid catalyst formed in situ is BF 3 •PhOH (Strategy A) or BF 3 •H 2 O (Strategy B) [29,30].…”

Electron Transfer Studies on Conjugated Ferrocenyl-Containing Oligomers

“…Metallopolymers possess interesting chemical, electrical, and magnetic properties; especially, metallocene-containing polymers have attracted considerable attention due to the unique properties that arise from their sandwich structures. − Since the discovery of ferrocene as the first sandwich compound in 1951, it has been the most intensively researched organometallic moiety . The incorporation of ferrocene into the polymer’s backbone led to novel electrochemical properties, such as pronounced electron-donating ability, fast electrochemical response, thermal stability, and redox reversibility, and thus a wide range of applications became accessible. ,− The group of Manners introduced ferrocenyl units into polymeric materials by thermal ring-opening polymerization (ROP) of strained silicon-bridged feroccenophanes to form high molar mass organometallic polymers . Furthermore, polymers with various bridging moieties such as boron, sulfur, silicon, CH 2 , and C 2 H 4 in the main chains of ferrocene-containing polymer backbones have been developed. , However, the backbone moieties of those polymers often lack conjugation, which hinders backbone-mediated electron transport throughout the polymer …”