Tetraphenylporphyrin, TPP

LB Films of Porphyrins and Phthalocyanines. The porphyrin is one of the most important among biomolecules. The most stable synthetic porphyrin is 5,10,15,20-tetraphenylporphyrin (TPP). Many porphyrin and phthalocyanine (PC) derivatives form good LB films. Both these molecules are important for appHcations such as hole-burning that may allow information storage using multiple frequency devices. In 1937 multilayers were built from chlorophyll (35). 

The singlet oxygenation of disiliranes 82a-f in benzene with tetraphenylporphyrin (TPP) as sensitizer gave cyclic peroxides 83a-f in 40-92% yields with a small amount of dioxasiletane 84a-f (Table 17)94,98,99... 

Robert and Meunier have isolated and characterized covalent adducts of metallopor-phyrins with artemisinin. Initial attempts using an iron(II) heme model were inconclusive, since the strong paramagnetism of the iron did not allow detailed characterization of the adduct and attempts at demetallation resulted in its degradation. Therefore, manganese(II) tetraphenylporphyrin (TPP) was used since it required milder demetallation conditions and the adduct 50a was formed. The suggested mechanism for the alkylation involves a pendent ethyl radical 50 (Scheme 13). 

A range of neutral, singly and doubly oxidized heteroleptic double-decker complexes of the type [M(IV)(P)(Pc)](n), where n = 0, +1, or +2, M=Zr or Hf, P = the dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP), and Pc = the dianion of phthalocyanine, has been reported. Each oxidized or reduced compound was characterized by UV-visible and/or EPR spectroscopy. The neutral compounds all undergo two reversible ring-centered oxidations and two reversible ring-centered reductions. The redox potentials were found to depend upon the type of macrocycle. They also vary with the size of metal ion in the case of oxidation but not in reduction, where E° values are relatively unaffected and shift by only 20-40 mV upon going from Hf(P)(Pc) to Th(P)(Pc), as compared to a much larger 220-280 mV shift between E° for the first oxidation of the same compounds [27]. 

Parallel studies were carried out cm the Co(ll)poiphyrin complexes91. We chose two porphyrin derivatives soluble in organic solvents protoporphyrin IX dimethyl-ester (PPME) 38, and tetraphenylporphyrin (TPP) 39. 

Synthetic iron porphyrin complexes such as Fe(TPP) (tetraphenylporphyrin = TPP), Fe(TMP) (Tetramesitylporphyrin = TMP), and Fe(TDCPP) (tetrakis (dichlorophenyl)porphyrin = TDCPP) (Fig. 9) have been used as models for P450 and peroxidase (9, 50-54). Early pioneering work showed that epoxida-tion catalyzed by Feln(TPP) was successfully carried out by the use of iodosylbenzene (Ph—1=0) as an oxidant (50). A very interesting feature of this model epoxidation is that the cis olefin is readily oxidized while the trans olefin is hardly oxidized (e.g., d.v-stylbene can be oxidized in 80% yield, but fraws-stylbene gave only a trace amount of the epoxide under the same conditions) (50, 55). Most of the model reactions are carried out in homogeneous organic solvents such as chloroform, dichloromethane, and acetonitrile, thus, the c/.v-epoxidation is expected to be a kinetically favorable process over the trans-epoxidation. 

Two new tetraphenylporphyrin (TPP) catalysts have been reviewed.331 Cr(TPP)m triflate is highly regio- and stereo-selective in rearranging epoxides into aldehydes, while the iron perchlorate analogue affords the corresponding ketones. 

In this paper, we present the results of an experimental study on the phase behavior of well-characterized binary mixtures which represent the more complex mixtures that arise in SCF extractions of petroleum residua and coal liquids. These binary mixtures consist of pentane and toluene with meso-tetraphenylporphyrin (TPP). Porphyrins occur naturally in crude oils (11,12) and represent an important class of high molecular-weight constituents of these oils, including those which contain heavy metals, such as nickel and vanadium. 

One drawback for the direct organocatalytic a-oxidation of aldehydes and ketones is the use of nitrosobenzene, which is an expensive oxygen source . This has led to further investigations in order be able to use other oxidants. Recently, Cordova et al. [20] reported that r-a-methyl proline could incorporate O2 in the a-position of an aldehyde. The presence of tetraphenylporphyrin (TPP) as sensitizer was necessary to promote the formation of singlet 02 as the electrophilic species. Although, the enantioselectivities obtained were only moderate (54-66% ee), this represents undoubtedly a very intriguing alternative to the use of nitrosobenzene in this type of reaction. 

Reaction Pathway and Products. In the presence of a catalytic amount of a tetraphenylporphyrin (TPP) Mn(III) complex (34) and sodium borohydride, treatment of cyclohexene with excess oxygen (air) in benzene-ethanol leads effectively to cyclohexanol and cy-clohexenol. The reaction is quite different from the known autoxidation catalyzed by TPP Mn(III) in the absence of NaBH4 (Figure 7). The most significant characteristics of the present TPPMn-NaBH4-02 reaction compared with the autoxidation are ... 

There are also a number of complexes with M—C—M bridges. For example, reduction of the tetraphenylporphyrin (tpp)FeCl by NaBH4 in CH2CI2 gives (tpp)Fe, which in turn, with CI4, gives [(tpp)Fe]2C as dark purple crystals. Mossbauer spectra indicate that this has FeIV and thus (tpp)Fe=C=Fe(tpp). 

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