NDLI: An iron-cyclopentadienyl bond cleavage mechanism for the thermal ring-opening polymerization of dicarba[2]ferrocenophanes

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Chemical Science Vol - 3 Issue - 2

Chemical Science Vol -2

Chemical Science Vol -1

An iron-cyclopentadienyl bond cleavage mechanism for the thermal ring-opening polymerization of dicarba[2]ferrocenophanes

Content Provider	Royal Society of Chemistry (RSC)
Author	Stonor, Andrew J. Chabanne, Laurent Manners, Ian Gilroy, Joe B. Haddow, Mairi F. Russell, Andrew D. Baljak, Sladjana
Copyright Year	2012
Abstract	In order to gain insight into the mechanism for the thermal ring-opening polymerization of strained dicarba[2]ferrocenophanes, the thermal reactivity of selected examples of these species with different substitution patterns has been explored. When heated at 300 °C dicarba[2]ferrocenophanes meso/rac-[Fe(η5-C5H4)2(CHPh)2] (mesomeso/racrac-7) and meso-[Fe(η5-C5H4)2(CHCy)2] (mesomeso-13) were found to isomerize or to undergo disproportionation, respectively. These processes are apparently general for dicarba[2]ferrocenophanes with one or more non-hydrogen substituents at each carbon atom in the dicarba bridge and both appear to involve homolytic cleavage of the C–C bond in the bridge as a key step. In striking contrast, derivatives containing either one or no non-hydrogen substituents on the bridge such as {Fe[η5-C5H4]2[CH(Ph)CH2]} (15) and [Fe(η5-C5H4)2(CH2)2] (17) undergo thermal ring-opening polymerization (ROP) under similar conditions (300 °C, 1 h). Thus, thermolysis of 15 yielded polyferrocenylethylene {Fe[η5-C5H4]2[CH(Ph)CH2]}n (16a) with a broad molecular weight distribution (Mw = 13,760, PDI = 3.27). Analysis of 16a by MALDI-TOF mass spectrometry suggested that the material was macrocyclic. Thermal treatment of linear polyferrocenylethylenes {Fe[η5-C5H4]2[CH(Ph)CH2]}n with narrow molecular weight distributions (prepared by photocontrolled ROP) at 300 °C confirmed that the macrocycles detected form directly, and not as a result of depolymerization. Copolymerizations of 15 with 17 and of 15 with the deuterated species [Fe(η5-C5H4)2(CD2)2] (dd44-17) were conducted in order to probe the bond cleavage mechanism. Comparative NMR spectroscopic analysis of the resulting copolymers 18 and dd44-18, respectively, and of homopolymer 16a, indicated that thermal ROP does not occur via a homolytic C–C bridge cleavage mechanism. A series of thermolysis experiments were conducted with MgCp2 (Cp = η5-C5H5) at 300 °C, which resulted in the isolation of ring-opened species formed from 15 and 17, and indicated that the Fe–Cp bonds can be cleaved under the thermal ROP conditions employed. The studies indicated that a chain growth process that involves heterolytic Fe–Cp bond cleavage in the monomers is the most probable mechanism for the thermal ROP of dicarba[2]ferrocenophanes.
Starting Page	830
Ending Page	841
Page Count	12
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	3
Issue Number	3
Journal	Chemical Science
DOI	10.1039/c1sc00566a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Disproportionation PDI Thermal decomposition Ionization Ring-opening polymerization Covalent bond Nuclear magnetic resonance spectroscopy Polymer Molar mass distribution Carbon Mass spectrometry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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