Olefin metathesis for metal incorporation: Preparation of conjugated ruthenium-containing complexes and polymers

Bolton, Sarah L.; Schuehler, Danielle E.; Niu, Xiang; Gopal, Lakshmi; Sponsler, Michael B.

doi:10.1016/j.jorganchem.2006.08.085

Cited by 12 publications

(9 citation statements)

References 43 publications

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“…However, as the initiation of the G3 complex is significantly faster than that of G2 , the stoichiometric reaction of G3 with conjugated polyolefins can lead easily to OMMI complexes. It has been reported by Sponsler and co‐workers that the reaction of G3 with hexatriene ( 65 ) followed by the addition of PCy 3 results in the formation of η 1 ‐allyl G2 derivative complex 67 (Scheme ) …”

Section: Synthesis and Investigation Of η1‐ And η3‐allyl Ruthenium Mementioning

confidence: 99%

Ruthenium‐Catalyzed Metathesis of Conjugated Polyenes

et al. 2016

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Abstract:In the past decade numerous examples of olefin metathesis-based chemical technologies have been developed making olefin metathesis increasingly dominant in several sustainable and green chemical processes. In spite of the wide application profile, conjugated olefin metathesis -especially conjugated polyene metathesis -is an area of great interest with little exploration. Metathesis of conjugated polyenes is often cumbersome and requires high catalyst loading, most probably due to formation of less or inactive ruthenium  3 -vinylcarbene intermediates. Mechanistic understanding and development of a new highly active catalytic system for olefin metathesis will open new areas for exploration. For example, the utilization of petrochemical by products such as cyclopentadiene or a new way in utilizing butadiene, isoprene and conjugated electron systems containing natural products such as terpenes and polyunsaturated fatty acids. Understanding the mechanism of ruthenium  1 - 3 -vinylcarbene interconversion may open the way to the development of new generation ruthenium-based latent metathesis catalyst systems. This review summarizes the most relevant pioneer work focused on metathesis of conjugated polyenes in order to open new ideas for the development of forthcoming latent metathesis catalysts and to explore different application areas.

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Section: Synthesis and Investigation Of η1‐ And η3‐allyl Ruthenium Mementioning

confidence: 99%

Ruthenium‐Catalyzed Metathesis of Conjugated Polyenes

et al. 2016

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“…2). 41, 42 We sought to use OMMI with the ultimate polyene, PA, to prepare MIPA, a new organometallic material (Scheme ). To achieve a high level of incorporation, G2B , which is active enough to react at disubstituted double bonds, was used.…”

Section: Resultsmentioning

confidence: 99%

“…Red-shifting is consistent with covalent attachment of the metal centers. 41 With increasing % [Ru], the spectra became blue-shifted, showing greater similarity to the spectrum of G2B (Fig. 5).…”

Section: Spectroscopymentioning

confidence: 86%

Ruthenium‐incorporated, metathesis‐active polyacetylene

Sherwood

Williams

Sponsler

2009

J. Polym. Sci. A Polym. Chem.

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Two olefin metathesis methods have been developed for the preparation of metal‐incorporated polyacetylene (MIPA) with high levels of covalently attached ruthenium complex. Treatment of freshly prepared, porous polyacetylene (PA) formed by polymerization of acetylene by the metathesis catalyst (H2IMes)RuCl2(CHPh)(3‐bromopyridine)2 (G2B) with additional G2B resulted in the incorporation of the ruthenium complex into the solid polymer in levels up to 75% by mass, giving two‐step MIPA (MIPA2). Alternatively, single‐step MIPA (MIPA1) samples with similar levels (up to 79% by mass) of ruthenium incorporation were obtained by polymerization of acetylene with highly concentrated solutions of G2B, and the resulting materials formed fine suspensions in CH2Cl2. A variety of experiments confirmed that both the methods give materials with ruthenium covalently attached to PA chains. Shiny, tough MIPA films were obtained by pressing the black powders obtained by either method. Some MIPA properties were dependent on the amount of metal incorporation, but even samples with high incorporation levels mimicked untreated PA in many respects. MIPA1, but not MIPA2, was made electrically conductive by doping with iodine. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1061–1072, 2009

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“…It has been reported by Sponsler and co-workerst hat the reaction of G3 with hexatriene (65)f ollowed by the addition of PCy 3 results in the formation of h 1 -allyl G2 derivativec omplex 67 (Scheme 31). [65]…”

Section: Scheme10 General Demonstration Of Cyclic Conjugated Diene Rmentioning

confidence: 99%