NDLI: Comparative Studies of Thermally Induced Homolytic CarbonCarbon Bond Cleavage Reactions of Strained Dicarba[2]ferrocenophanes and Their Ring-Opened Oligomers and Polymers

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Comparative Studies of Thermally Induced Homolytic CarbonCarbon Bond Cleavage Reactions of Strained Dicarba[2]ferrocenophanes and Their Ring-Opened Oligomers and Polymers

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Comparative Studies of Thermally Induced Homolytic CarbonCarbon Bond Cleavage Reactions of Strained Dicarba[2]ferrocenophanes and Their Ring-Opened Oligomers and Polymers

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Gilroy, Joe B. Russell, Andrew D. Manners, Ian
Description	Author Affiliation: Russell AD ( School of Chemistry, University of Bristol, Cantocks' Close, Bristol BS8 1TS (UK).)
Abstract	Reactivity studies of dicarba[2]ferrocenophanes and also their corresponding ring-opened oligomers and polymers have been conducted in order to provide mechanistic insight into the processes that occur under the conditions of their thermal ring-opening polymerisation (ROP) (300 °C). Thermolysis of dicarba[2]ferrocenophane $rac-[Fe(η^{5}-C_{5}H_{4})_{2}(CHPh)_{2}]$ (rac-14; 300 °C, 1 h) does not lead to thermal ROP. To investigate this system further, rac-14 was heated in the presence of an excess of cyclopentadienyl anion, to mimic the postulated propagating sites for thermally polymerisable analogues. This afforded acyclic $[(η^{5}-C_{5}H_{5})Fe(η^{5}-C_{5}H_{4})-CH_{2}Ph]$ (17) through cleavage of both a FeCp bond and also the CC bond derived from the dicarba bridge. Evidence supporting a potential homolytic CC bond cleavage pathway that occurs in the absence of ring-strain was provided through thermolysis of an acyclic analogue of rac-14, namely $[(η^{5}-C_{5}H_{5})Fe(η^{5}-C_{5}H_{4})(CHPh)_{2}-C_{5}H_{5}]$ (15; 300 °C, 1 h), which also afforded ferrocene derivative 17. This reactivity pathway appears general for post-ROP species bearing phenyl substituents on adjacent carbons, and consequently was also observed during the thermolysis of linear polyferrocenylethylene $[Fe(η^{5}-C_{5}H_{4})_{2}(CHPh)_{2}]_{n}$ (16; 300 °C, 1 h), which was prepared by photocontrolled ROP of rac-14 at 5 °C. This afforded ferrocene derivative $[Fe(η^{5}-C_{5}H_{4}CH_{2}Ph)_{2}]$ (23) through selective cleavage of the H(Ph)CC(Ph)H bonds in the dicarba linkers. These processes appear to be facilitated by the presence of bulky, radical-stabilising phenyl substituents on each carbon of the linker, as demonstrated through the contrasting thermal properties of unsubstituted linear trimer $[(η^{5}-C_{5}H_{5})Fe(η^{5}-C_{5}H_{4})(CH_{2})_{2}(η^{5}-C_{5}H_{4})Fe(η^{5}-C_{5}H_{4})(CH_{2})_{2}(η^{5}-C_{5}H_{4})Fe(η^{5}-C_{5}H_{5})]$ (29) with a $H_{2}CCH_{2}$ spacer, which proved significantly more stable under analogous conditions. Evidence for the radical intermediates formed through CC bond cleavage was detected through high-resolution mass spectrometric analysis of co-thermolysis reactions involving rac-14 and 15 (300 °C, 1 h), which indicated the presence of higher molecular weight species, postulated to be formed through cross-coupling of these intermediates.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	14
Volume Number	20
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2014-04-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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