Cellulose-Based Polymers with Long-Chain Pendant Ferrocene Derivatives as Organometallic Chromophores

The inclusion of organometallic units into polymeric structures has attracted much attention in different fields according to the nature and behaviour of the inserted metal. Moreover, the discovery of organometallic polymers and their structural characterization initiated an explosive rebirth of organometallic chemistry. Organometallic moieties are in or pendent to the polymer backbone and examine some of the uses of the emergent metallocene polymers, and new uses are still being found for these remarkable organometallic moieties. This review gives a simple introduction to variable organometallic molecules and their characteristics. This review will focus on the syntheses and characterization of organometallic polymers, including ferrocene-and phosphorus-containing polymers. A general overview on ferrocene polymers with a special attention to ferrocene-containing liquid crystalline polymers (including a ferrocene moiety in the main chain, side-chain or dendrimers) and fullerene-ferrocene liquid crystalline polymers is presented. In addition, more details for synthesis and properties of phosphorus-containing polymers are illustrated.

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“…Four years more, both thermotropic and lyotropic ferrocenyl containing cellulose derivatives 47 were found by Zhang et al [123] (Fig. 30).…”

Section: Ferrocene Moieties In Side-chain Liquid Crystalline Polymersmentioning

confidence: 86%

Organometallic Ferrocene- and Phosphorus-Containing Polymers: Synthesis and Characterization

Hussein

Asiri

2012

Designed Monomers and Polymers

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“…Thus, we focussed our attention on the introduction of a linkage with the aim of avoiding decomposition under the acidic conditions required for the attachment. Direct alkylation of (R)-8 with BrA C H T U N G T R E N N U N G (CH 2 ) 6 OTIPS [13] gave the TIPS-protected alcohol 10, albeit in low yield (44 %). Alternatively, one can take advantage of the easy formation of ferrocenylmethyl carbocations from ferrocenylmethanol derivatives in the presence of acid.…”

Section: Synthesis and Immobilization Of Chiral Fesulphostype Ligandsmentioning

confidence: 99%

“…Flash chromatography was carried out on 60 (35-70 mm) silica gel. 1 H and 13 C NMR spectra were recorded at 300 MHz and and 75 MHz, respectively. Enantiomeric excess and diastereomeric excess were determined by HPLC.…”

Section: Experimental Section General Remarksmentioning

confidence: 99%

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Synthesis of Polymer‐Supported Fesulphos Ligands and their Application in Asymmetric Catalysis

et al. 2007

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Abstract:The synthesis of two Fesulphos-based chiral ligands and their immobilization on a polystyrene support is described. These supported chiral ligands act as very efficient catalysts in 1,3-dipolar cycloaddition and allylic substitution reactions providing the products with excellent enantioselectivities (91 to > 99 % ee). Filtration of the catalyst from the reaction mixtures allows simple product isolation. The polymer-supported Cu complex of chiral ligand PS-8 can be recycled without further addition of a copper salt in 1,3-dipolar cycloaddition reactions.

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“…Recently, organometallic complexes were grafted to functionalized cellulose for potential application in nonlinear optic. 4 Chiral pyridine-bis(oxazoline) (Pybox) ligands complexed to ruthenium are very efficient in cyclopropanation reaction of alkenes with diazoesters. 5 Pybox ligands have been supported onto silica 6 and polymers 7 via grafting or copolymerized with styrene and divinylbenzene.…”

mentioning

confidence: 99%

Immobilization of Pybox Ligand on Modified Starch

Cornejo¹,

Martínez‐Merino²,

Gil³

et al. 2005

Chemistry Letters

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Starch, one of the most abundant natural polymer was used as support for chiral pyridine-bis(oxazoline) ligand. The corresponding ruthenium complex was used as catalyst in cyclopropanation reaction of styrene with ethyl diazoacetate. Yield, diastereoisomeric excess and enantiomeric excess kept constant after 3 runs.The preparation of tethered organometallic complexes to perform enantioselective synthesis has been reported over several types of supports. Most commonly chiral catalysts were immobilized over solid support through covalent bondings. 1Ligands have been covalently grafted to inorganic materials such as amorphous silica or mesoporous structured inorganic solid. They can also be introduced in organic polymers either by modification of Merrifield type resin or by copolymerisation. On the other hand, natural polymers such as polysaccharides are largely available on great scale and can be applied as support of molecular catalysts. In this sense, the starch is a particularly attractive molecule: its swelling is strongly affected by the nature of the solvent. Moreover, it is very cheap and not toxic. Few reports are dealing with the use of polysaccharides as support for organometallic species. Allylic substitution was performed with Pd/TPPTS complex entrapped in different polysaccharides. Silica-supported starch-polysulfosiloxane-Pt complexes were used for asymmetric hydrogenation of 4-methyl-2-pentanone to 4-methyl-2-pentanol with 94% ee. 3 In that approach, the intrinsic chirality of the starch was responsible of the enantioselectivity. Recently, organometallic complexes were grafted to functionalized cellulose for potential application in nonlinear optic. 4Chiral pyridine-bis(oxazoline) (Pybox) ligands complexed to ruthenium are very efficient in cyclopropanation reaction of alkenes with diazoesters. 5 Pybox ligands have been supported onto silica 6 and polymers 7 via grafting or copolymerized with styrene and divinylbenzene. 8 These studies showed that the nature of the support played a significant role on the activity of the supported catalyst as well as on the enantioselectivity of the reaction. 9 To our knowledge, carbohydrate type solids have not been developed as supports for chiral catalysts, and this could be of interest because the additional chirality of the support. Thus, the aim of this work was the covalent grafting of Pybox ligands to starch and their test in the asymmetric cyclopropanation benchmark reaction (ACP). In order to get high flexibility of the catalyst over the support, it is necessary to insert a long chain as a linker between the starch and the ligand. We previously reported palladium-catalyzed telomerization of starch with butadiene.10 This transformation allowed the introduction of a 8-carbons chain in starch. Owing to the presence of unsaturated double bonds in the lateral chain, subsequent functionalization is conceivable. In this paper, we reported the grafting of a Pybox ligand to a telomerized starch and the preliminary results in asymmetric cyclopropanation reaction.Tre...

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Cellulose-Based Polymers with Long-Chain Pendant Ferrocene Derivatives as Organometallic Chromophores

Cited by 19 publications

References 42 publications

Organometallic Ferrocene- and Phosphorus-Containing Polymers: Synthesis and Characterization

Organometallic Ferrocene- and Phosphorus-Containing Polymers: Synthesis and Characterization

Synthesis of Polymer‐Supported Fesulphos Ligands and their Application in Asymmetric Catalysis

Immobilization of Pybox Ligand on Modified Starch

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