NDLI: Photocontrolled Ring-Opening Polymerization of Strained Dicarba[2]Ferrocenophanes: A Route to Well-Defined Polyferrocenylethylene Homopolymers and Block Copolymers

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Photocontrolled Ring-Opening Polymerization of Strained Dicarba[2]Ferrocenophanes: A Route to Well-Defined Polyferrocenylethylene Homopolymers and Block Copolymers

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Mayer, Ulrich F. J. Lough, Alan J. Manners, Ian Gilroy, Joe B. López-gómez, María J. Herbert, David E. Charmant, Jonathan P. H.
Description	Author Affiliation: Herbert DE ( School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.)
Abstract	The ring-opening polymerization (ROP) behavior of a variety of substituted 1,1′-ethylenylferrocenes, or dicarba[2]ferrocenophanes, is reported. The electronic absorption spectra and tilted solid-state structures of the monomers $rac-[Fe(η^{5}-C_{5}H_{4})_{2}(CHiPr)_{2}]$ (7), $[Fe(η^{5}-C_{5}H_{4})_{2}(C(H)MeCH_{2})]$ (8), and $rac-[Fe(η^{5}-C_{5}H_{4})_{2}(CHPh)_{2}]$ (9) are consistent with the presence of substantial ring strain, which was exploited to synthesize soluble, well-defined polyferrocenylethylenes (PFEs) $[Fe(η^{5}-C_{5}H_{4})_{2}(C(H)MeCH_{2})]_{n}$ (12) and $[Fe(η^{5}-C_{5}H_{4})_{2}(CHPh)_{2}]_{n}$ (13) through photocontrolled ROP. Polymer chain lengths could be controlled by the monomer-to-initiator ratio up to about 50 repeat units and, consistent with the “living” nature of the polymerizations, sequential block copolymerization with a sila[1]ferrocenophane led to polyferrocenylethylene–polyferrocenylsilane (PFE-b-PFS) block copolymers (14 and 15). PFE polymers 12 and 13 showed two reversible oxidation waves, indicative of appreciable Fe⋅⋅⋅Fe interactions along the polymer backbone. The diblock copolymers were characterized by NMR spectroscopy, GPC analysis, and cyclic voltammetry.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	45
Volume Number	15
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2009-11-16
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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