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A review on the prepn. and uses of organometallic polymers having metal-carbon bonds in the main or side chains or heteroatom-metal bonds in the main chain.
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The living ring-opening metathesis polymns. of deltacyclene (I) and 5-(tert-butyldimethylsiloxy)deltacyclene (II) in presence of the Schrock catalyst Mo(=CHCMe2Ph)[=N-2,6-(iso-Pr)2Ph](O-tert-Bu)2 were described. II was prepd. by first epoxidizing I, then treating this epoxide with a Lewis acid in pr...
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Organoiron polynorbornene containing arylazo or hetarylazo dye chromophores has been prepared via ring opening metathesis polymerization using Grubbs' catalyst. The obtained polymers were isolated as brightly colored materials and displayed good solubility in polar organic solvents. The colors of th...
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As functionalization of the polynorbornene backbone has shown to be a viable route towards altering the thermal and chem. properties of the resulting polymeric material, our focus was on the prepn. of norbornene monomers contg. a side-chain consisting of a rigid mesogen and/or an aliph. spacer. Ring...
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Novel polynorbornenes containing cationic cyclopentadienyliron moieties pendent to the polymer side chains were prepared via polymerization of metallated norbornene monomers using Grubbs' catalyst. Thermogravimetric analysis of the organometallic polymers showed two weight loss steps: the first at 2...
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A number of red to violet thienyl-2-azo and thienyl-5-azo disperse dyes were prepared using Gewald's methodology. Structural characterization of these novel dyes was carried out using IR, NMR and mass spectroscopy. UV–visible studies of these azo dyes in a number of polar solvents showed a conside...
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The synthesis of the title complex was achieved via the reaction of a η6-p-dichlorobenzene-η5-cyclopentadienyliron cation with an organic four-arm core to produce the tetrairon complex. This tetrairon-containing core was subsequently polymerized via nucleophilic aromatic substitution with various ...
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In the title compd., [Fe(C13H11O2)2], there are markedly different orientations of the two phenylmethoxycarbonyl substituents [O-C-C-C torsion angles = 84.5(3) and 139.6(2)°]. These orientations are mediated by a no. of intermol. C-H···O interactions, which result in a one-dimensional hy...
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Polyethers and/or thioethers contg. organoiron moities in either the backbone or the side chain were prepd. under mild reaction conditions. Polysiloxanes contg. arene cyclopentadienyliron or ferrocene moieties were also prepd. and their morphol. thermal and spectroscopic characterizations were examd...
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Ferrocene-based monomers were prepd. via the reaction of cationic chloroarene cyclopentadienyliron complex cations with 1,1'-ferrocene dicarbonyl chloride. These monomers were then reacted with O-, S- and N- contg. dinucleophiles to give the polymeric materials with neutral iron moieties in the back...
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The kinetics involved in the thermal degradation of an aryl azo dye-containing polynorbornene was investigated by using isothermal DSC data. The activation energy of the degradation was found to be temperature dependent with two different values of 140 ± 5 and 21 ± 2 kJ mol−1, and the Avrami exp...
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A general method for the synthesis of some arylated phenylsulphonylacetonitriles 6a–g, 10a, b and 16 and ethyl cyanoacetates 7a-d and 11a, b is described. Nucleophilic substitution of the cyclopentadienyliron complexes of chloroarenes 1a–g with phenylsulphonylacetonitrile 2 or ethyl cyanoacetate...
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Isomeric dichlorobenzene complexes of ironcyclopentadienyl and pentamethylcyclopentadienyl- ruthenium were used to facilitate nucleophilic arom. substitution (SNAr) reactions with a variety of O, S, and N contg. nucleophiles. Oligomeric and polymeric systems were achieved by variation in the ratio o...
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Hydride and cyanide addn. to di- and polycyclopentadienyliron arene complex cations with etheric bridges is described. Reaction of the di-Fe complexes with NaBH4 gave a no. of adducts. P-Methyl- and o,o-dimethylphenoxybenzene cyclopentadienyliron complexes were used as models in this study to allow ...
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Double nucleophilic substitution of 1,2-, 1,3-, or 1,4-(HO)2C6H4 with [(η5-C5H5)Fe(η6-C6H5Cl)]+ PF6- (anion assumed) and K2CO3 in THF/DMF afforded the corresponding bis(cyclopentadienyliron) arom. ether complexes I, isolated as PF6- salts. Compds. I and biphenyl analogs were prepd. in 70-95% y...
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Nucleophilic aromatic substitution of isomeric chlorotoluenes complexed to the cyclopentadienyliron moiety with ethyl cyanoacetate in the presence of K2CO3 in DMF results in the formation of the isomeric ethyl tolylcyanoacetate complexes. Photolysis of these complexes leads to the formation of the t...
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Our research interests have been focused on the design of new monomeric and polymeric materials using organoiron complexes as precursors. Cyclopentadienyliron chloroarene complexes were used to mediate the synthesis of sulfide contg. compds. These compds. were designed with various arom. and aliph. ...
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Potassium fluoride - Celite has been found to be an effective heterogeneous catalyst in arylation of 1,3-dicarbonyl compounds with substituted arenes activated by π-complexation with the ironcyclopentadienyl moiety.
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The synthesis of cationic organoiron polymers with azobenzene moieties in their side chains has been accomplished via nucleophilic aromatic substitution and ring-opening metathesis polymerization (ROMP) reactions. Polyaromatic ethers and thioethers with azobenzene moieties in their side chains were ...
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A series of star-shaped macromolecules bearing distinct symmetrical branches with alternating organoiron complexes and azobenzene moieties were synthesized using both convergent and divergent approaches. The various azo dye and organoiron-containing branches were reacted with multifunctional cores v...
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There has been tremendous interest in organoiron macromols. This interest stems from their application as chem. sensors, electrocatalysts, modified electrodes and photo-active mol. devices. Herein, we report the synthesis and characterization of a no. of different classes of organoiron macromols. co...
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A review. This chapter discusses the synthesis, structures, selected properties, and uses of polymers that have metal-metal bonds incorporated into their backbone chains. These materials are of interest for a no. of reasons. The primary reason is the promise of new and unusual properties. In particu...