Phenols substituted , complexes

Tetra(o-aminophenyl)porphyrin, H-Co-Nl TPP, can for the purpose of electrochemical polymerization be simplistically viewed as four aniline molecules with a common porphyrin substituent, and one expects that their oxidation should form a "poly(aniline)" matrix with embedded porphyrin sites. The pattern of cyclic voltammetric oxidative ECP (1) of this functionalized metal complex is shown in Fig. 2A. The growing current-potential envelope represents accumulation of a polymer film that is electroactive and conducts electrons at the potentials needed to continuously oxidize fresh monomer that diffuses in from the bulk solution. If the film were not fully electroactive at this potential, since the film is a dense membrane barrier that prevents monomer from reaching the electrode, film growth would soon cease and the electrode would become passified. This was the case for the phenolically substituted porphyrin in Fig. 1. 

The axial immobilization of chiral [Mn((S,S)-salen )j (where salen = (Si,Sj-NiN -bis(3,5-diR -salicylidene)-l,2-diRbethane-diamine R = Bu, R -R = -(CH2)4- R = Bu, R = Ph R = Pn, R R = -(CH2)4-) complexes was achieved by reaction of [Mn(salen )Cl] with sulfonic acid- or phenol-substituted crosslinked and insoluble polystyrene resins [45]. The resulting polymer-immobilized [Mn(salen )j complexes were active and enantioselective for the asymmetric epoxidation of... 

Z)-Phenol-substituted alkenes (67) can be produced by the palladium(0)-catalysed reaction of propargylic oxiranes (66) with phenols. This regio- and stereo-selective (g) addition is believed to occur via the formation of 7t-propargyl- and Tr-allylpalladium complexes. The phenoxy-substituted enones were obtained as by-products and their proportion depended on the reaction conditions.75... 

The phenol substituted [9]aneN3 derivative H2L22 (Fig. 24) also forms a dinuclear zinc complex ion with the formula [Zn2(HL22)20H], in which one phenol from each ligand is deprotonated. The two zinc atoms are linked by one /ii-hydroxo bridge supported by two hydrogen bonds between the phenol on one macrocycle and the phenolate of the second. The Zn—Zn distance is 3.55 A (106). 

We also mention that the ionized phenol-water complex has been observed and examined in depth" . Complexes of phenol radical cation with ammonia" and molecular nitrogen have also been produced. The existence of an intramolecular hydrogen bond in orf/zo-substituted phenol radical cations has also been demonstrated . 

Phenol-ketone novolacs 1487, 1488 Phenol-nitrile complexes 377 Phenol radical cations 1101 fragmentation of 289-291 Phenols—see also Biphenols, Bis-phenols, Hydroxybenzenes, Polyphenols acidities of, gas-phase 310-312 acylation of 629-632, 933, 934 Lewis acid catalyzed 631 montmoriUonite-catalyzed 632 pyridine-catalyzed 631 adsorption of 944 alkylation of 606-629, 941 Brdnsted acid catalyzed 612 Lewis acid catalyzed 607-611 solid acid catalyzed 612-621 stereoselective 621-626 under supercritical conditions 621 as antioxidants 139-143, 840-901 ort/io-substituted 845 thermochemistry of 139, 140, 179 autoxidation of 1118, 1119 bromination of 649-651 jr-cation interaction of 322 chlorination of 649 comparison with isoelectronic methyl, amino and fluoro aromatic derivatives 226... 

Star-shaped molecules containing cationic arene complexes of iron and ruthenium have been reported by Astruc and co-workers.298 Utilizing the activating nature of the cyclopentadienyliron moiety on the complexed arene, 260 was converted into 262 via bromobenzylation. The photolysis of 262 gave 263, which was subsequently reacted with 264 to give the hexametallic complex 265. Further nucleophilic aromatic substitution reactions with phenol 266 gave the allyl-substituted complex 267 (Scheme 2.70). 

Recent work indicates that the anion of the 3-hydroxyl group rather than the anion of the 2-hydroxyl group is the nucleophile. NMR studies of phenol-inclusion complexes [46] and the determination that the tosylation reaction of cyclodextrin takes place under basic conditions [47] lead to the conclusion that substitution occurs exclusively at the 3-position. 

Phosphorus(V) in its most stable oxidation state forms robust chelate complexes with the porphyrin, and retains the capability of binding two oxygen ligands in a frans-axial mode as outlined in Sect. 3. This strategy was used by Maiya [81,102-104] and Tanaka and Segawa [105]. The coordination chemistry of phosphorous(V) porphyrins is similar to germa-nium(IV), tin(IV), gallium(III), and aluminium(III) porphyrin coordination chemistry [102,106]. These metalloporphyrins were shown to form multiporphyrin complexes with phenol-substituted porphyrins. Because of the... 

The data in Figure 2 clearly show that the phenolic model compounds studied here are more reactive than monomeric phenol under standard phenol formaldehyde reaction conditions. This is not surprising, since a wealth of literature shows the phenols substituted with electron donating groups are more reactive than unsubstituted phenol (12-14). However, it is particularly important for these complex phenolic-rich pyrolysis oils. These results suggest that the pyrolysis oil phenolic will react rapidly under standard cooking conditions and become covalently bound into the polymer networic. This means that the pyrolysis oils contribute to the strength of the network and do not simply act as fillers or extenders. 

The chemical properties of the naphthaleneols are similar to those of phenol and resorcinol, with added reactivity and complexity of substitution... 

Platinum-group metals (qv) form complexes with chelating polymers with various 8-mercaptoquinoline [491-33-8] derivatives (83) (see Chelating agents). Hydroxy-substituted quinolines have been incorporated in phenol—formaldehyde resins (84). Stannic chloride catalyzes the condensation of bis(chloromethyl)benzene with quinoline (85). 

The following compounds have been obtained from thiete 1,1-dioxide Substituted cycloheptatrienes, benzyl o-toluenethiosulfinate, pyrazoles, - naphthothiete 1,1-dioxides, and 3-subst1tuted thietane 1,1-dioxides.It is a dienophile in Diels-Alder reactions and undergoes cycloadditions with enamines, dienamines, and ynamines. Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH2=CHCH=SQ2). which undergoes cyclo-additions to strained olefinic double bonds, reacts with phenol to give allyl sulfonate derivatives or cyclizes unimolecularly to give an unsaturated sultene. - Platinum and iron complexes of thiete 1,1-dioxide have been reported. 

Using the processes described above, complex products are obtained if a monosubstituted phenol is used instead of a 2,6-substituted material. However, by using as the amine" a 2-disubstituted pyridine such as 2-amylpyridine, more linear and, subsequently, useful polymers may be obtained. 

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