Sodium complexes porphyrins

Mechanisms of micellar reactions have been studied by a kinetic study of the state of the proton at the surface of dodecyl sulfate micelles [191]. Surface diffusion constants of Ni(II) on a sodium dodecyl sulfate micelle were studied by electron spin resonance (ESR). The lateral diffusion constant of Ni(II) was found to be three orders of magnitude less than that in ordinary aqueous solutions [192]. Migration and self-diffusion coefficients of divalent counterions in micellar solutions containing monovalent counterions were studied for solutions of Be2+ in lithium dodecyl sulfate and for solutions of Ca2+ in sodium dodecyl sulfate [193]. The structural disposition of the porphyrin complex and the conformation of the surfactant molecules inside the micellar cavity was studied by NMR on aqueous sodium dodecyl sulfate micelles [194]. 

Diazoalkanes are u.seful is precursors to ruthenium and osmium alkylidene porphyrin complexes, and have also been investigated in iron porphyrin chemistry. In an attempt to prepare iron porphyrin carbene complexes containing an oxygen atom on the /(-carbon atom of the carbene, the reaction of the diazoketone PhC(0)C(Ni)CH3 with Fe(TpCIPP) was undertaken. A low spin, diamagnetic carbene complex formulated as Fe(TpCIPP)(=C(CH3)C(0)Ph) was identified by U V-visible and fI NMR spectroscopy and elemental analysis. Addition of CF3CO2H to this rapidly produced the protonated N-alkyl porphyrin, and Bit oxidation in the presence of sodium dithionitc gave the iron(II) N-alkyl porphyrin, both reactions evidence for Fe-to-N migration processes. ... 

Chemical analysis revealed that commercial food grade copper chlorophyllin is not a single, pure compound, but is a complex mixture of structurally distinct porphyrins, chlorin, and non-chlorin compounds with variable numbers of mono-, di-, and tri- carboxylic acid that may be present as either sodium or potassium salts. Although the composition of different chlorophyllin mixtures may vary, two compounds are commonly found in commercial chlorophyllin mixtures trisodium Cu (II) chlorin Cg and disodium Cu (II) chlorin which differ in the number of... 

The trans effects on rr-acceptor ligands in Fe11 and Ru11 porphyrins are compiled in Table 14 and behave as expected according to transmission paths D or E (Fig. 1). Some deviations may be caused by comparison of values from different sources. The only notable features are the abnormally low values of the CO-stretching frequencies found in the sodium salt of a thiolatoiron(II)carbonyl, Na[Fe(TpivPP)CO(SMe)] (Series e, 120), and in the porphodimethene complex, Fe(OEPMe2)CO(l-MeIm) ([54] ... 

Although anionic polymerization of cyclic ethers is generally limited to oxiranes, there are reports of successful oxetane and tetrahydrofuran polymerizations in the presence of a Lewis acid. Aluminum porphyrin alone does not polymerize oxetane, but polymerization proceeds in the presence of a Lewis acid [Sugimoto and Inoue, 1999]. Similarly, THF is polymerized by sodium triphenylmethyl in the presence of a Lewis acid such as aluminum alkoxide [Kubisa and Penczek, 1999]. The Lewis acid complexes at the ether oxygen, which weakens (polarizes) the carbon-oxygen bond and enhances nucleophilic attack. 

The conjugation in the molecular wire may be disrupted or modulated to create systems with different properties. For example, a porphyrin Ceo donor-acceptor system linked with a conjugated binaphthyl unit, has a preference for the atropi-somer where the fullerene unit is closer to the porphyrin system, thus increasing the through space interactions [82]. The charge transfer process on a dyad containing a crown ether in the linker structure can be modulated by complexation/ decomplexation of sodium cations [83] but even more interesting is the construction of supramolecular systems where the donor and acceptor moieties are... 

The rhodium complex [CpRh(bipy)Cl2] is reported (162) to act as one-half of a redox couple that, in concert with a manganese porphyrin system, catalyzes the epoxidation of olefins by dioxygen. In this two-phase system, the aqueous phase contains sodium formate, and the organic phase is a trichloroethane solution of [Mnm(tpp)]1+ and the rhodium complex (tpp = meso-tetraphenylporphyrin). Apparently, the rhodium complex catalyzes the reduction of [Mnin(tpp)]1+ by formate, and the manganese(II) species thus formed binds dioxygen and reacts with the substrate olefin to form the epoxide. However, the intermedi-... 

Complexes of acetylacetone (acacH), benzoylacetone (bzacH) and dipivaloylmethane (dpmH) have been reported. The acetylacetonate [Cr(acac)2] has been prepared from chromium(II) acetate and acetylacetone.142,143 It can also be obtained by the addition of aqueous sodium acetylacetonate to an aqueous solution of chromium(II) chloride, but in any preparation the yellow solid must be filtered off and dried as rapidly as possible, otherwise the chromium(III) compound is obtained. Its magnetic moment is 4.99 BM at room temperature consistent with a high-spin d4 configuration. 142The powerful reducing ability of [Cr(acac)2] has been used to prepare iron(II) and chromium(II) complexes80 of porphyrins and related ligands. 

Sc(OEP)C>2CMe is 0.4 s, which is the longest for any porphyrin, while the fluorescent yield of 0.2 is very high. The radiative properties are explained in terms of covalent interactions between the metal and the ring as modified by the probable location of the metal ion above the porphyrin plane.24 Scandium OEP complexes are reduced to the a, y-dihydro derivatives on reduction with sodium anthracenide and methanol.25 The redox potentials of Sc(OEP)OH have been determined by cyclic voltammetry to be ligand oxidation in PrCN, 1.03 and 0.70 ligand reduction in DMSO, —1.54 (Ey2 values in V vs. SCE) no metal redox wave was observed.26... 

Chlorins (2) are undoubtedly the most important dihydroporphyrins, since the chlorin chromophore is found in chlorophylls and some bacteriochlorophylls and, as the magnesium complex, is the catalyst in photosynthesis. The method of choice for formation of trans-chlorins involves reduction of iron porphyrins with sodium in boiling isopentyl alcohol (57JCS3461), but methods involving photochemical reduction of tin(IV) porphyrins, isomerization of phlorins, reduction of metalloporphyrins with sodium anthracenide followed by protonolysis, heating with sodium ethoxide, and photoreductions of zinc(II) porphyrins in the presence of ascorbic acid have also been employed. The best method for formation of c/s-chlorins (note that all natural chlorophylls possess the trans arrangement) appears to... 

Alkali metals form porphyrin complexes of the type M2(Por) when their alkoxides are heated with porphyrin in dry pyridine, but are readily hydrolyzed.17 The transmetallation experiments indicate the stability of M2(Por) in the order K < Na < Li (Using radioactive sodium. Na2(TPP) is shown to undergo rapid metal exchange with Nal in pyridine (equation 2). 

Fe (Por)] is formed when Feni(Por) or Feu(Por) is electrochemically reduced or treated with a stoichiometric amount of sodium anthracenide in THF.89 [Fe TTP]" (Na-18-crown-6)+ (THF)2 is a tow-spin square planar complex jitK 2.5 BM, g x 2.1, 1.9, Fe—Npor 2.023(5) A), and shows a similar visible spectrum to that of Fe (TPP) but with a much lower intensity. This species is isoelectronic to Co (Por), the anionic charge, in addition to an odd electron to the dzl orbital, diminishes the ligand affinity of the iron atom. Further reduction generates an Fe"-porphyrin dianion. 

Sapphyrins (39) are metallated with divalent metal aoetates in the presence of sodium acetate (Scheme 109).274 For the Zn11 and Co11 complexes, structure (44) was proposed with the dianionic macrocycle coordinating to the metal ion as a tetradentate ligand. These metallosapphyrins experience ring contraction to porphyrin complexes under mass spectral conditions. 

With these highly oriented porphyrins regioselective oxidations were performed using the iron(III)- and manganese (Ill)-complexes 183 and 184, respectively, in the presence of sodium periodate, PhIO or 02/ascorbate. 

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