Meso-tetrakis

Decomposition of diazo compounds by iron porphyrins is a convenient method for the synthesis of non-heteroatom carbene-iron porphyrins [22]. Reaction of [Fe(F2o-TPP)] [F20-TPP = meso-tetrakis(pentafluorophenyl)porphyrinato dianion] with diazo compounds N2C(Ph)R (R = Ph, C02Et, C02CH2CH=CH2) under an inert atmosphere afforded complexes [Fe(F2o-TPP)C(Ph)R] in 65-70% yields (Scheme 2). Like the halocarbene complex [Fe(TPP)(CCl2)], [Fe(F2o-TPP)CPh2] reacted with Melm to afford six-coordinate species [(MeIm)Fe(F2o-TPP)CPh2] in 65% isolated yield. 

Fig. 3. Haptens and multivalent antigens prepared in this syudy. The viologen derivative, 4,4 -bipyridinium, l-(carboxypentyl)-l -methyl-dichloride (1), divalent antigen 2, and trivalent antigen 3. Anti-porphyrin antibodies were elicited for [5-(4-carboxyphenyl)-10,15,20-tris-(4-methylpyridyl)]porphine (3MPylC) or meso-tetrakis(4-carboxyphenyl)porphine (TCPP). meso-Tetrakis(4-methylpyridyl)porphine (TMPyP) was used to investigate the specificity of the antibody dendrimer for porphyrins...

Kndr, G. (2001) Intramolecular charge transfer excitation of meso-tetrakis (1-pyrenyl) porphyrinatogold(lll) acetate. Photosensitized oxidation of guanine. Inorganic Chemistry Communications,... 

Lebold TP, YeowEK, Steer RP (2004) Fluorescence quenching of the SI andS2 states of zinc meso-tetrakis(4-sulfonatophenyl)porphyrin by halide ions. Photochem Photobiol Sci 3 ... 

A number of metal porphyrins have been examined as electrocatalysts for H20 reduction to H2. Cobalt complexes of water soluble masri-tetrakis(7V-methylpyridinium-4-yl)porphyrin chloride, meso-tetrakis(4-pyridyl)porphyrin, and mam-tetrakis(A,A,A-trimethylamlinium-4-yl)porphyrin chloride have been shown to catalyze H2 production via controlled potential electrolysis at relatively low overpotential (—0.95 V vs. SCE at Hg pool in 0.1 M in fluoroacetic acid), with nearly 100% current efficiency.12 Since the electrode kinetics appeared to be dominated by porphyrin adsorption at the electrode surface, H2-evolution catalysts have been examined at Co-porphyrin films on electrode surfaces.13,14 These catalytic systems appeared to be limited by slow electron transfer or poor stability.13 However, CoTPP incorporated into a Nafion membrane coated on a Pt electrode shows high activity for H2 production, and the catalysis takes place at the theoretical potential of H+/H2.14... 

Subsequently, other publications have appeared involving the DA reactions of porphyrins with other dienes. For instance, the reaction of meso-tetrakis(pentafluorophenyl)porphyrin Id with the diene generated from pyrrole-fused 3-sulfolene gave rise to the isoindole-fused chlorin derivative 8 accompanied by a mixture of stereoisomeric bacteriochlorins 9 (Scheme 2) <98CC2355>. 

TPPS = meso-tetrakis(p-sulfonatophenyl)porphine TMPyP = meso-tetrakis(A/ methyl-4pyridyl)porphine TMPS = meso-tetrakis(sulfonatomesityl)porphine... 

More recently, Cavaleiro et al. described a new method to prepare novel glyco-dihydro- and diglycol-tetrahydroporphyrins (chlorins 116, 117, bacteriochlorins 119 and isobacteriochlorins 118), through CuCl-catalyzed cyclopropanation reactions of a-diazoacetates derived from di-acetonides of several glycosides 113bA-bD with meso-tetrakis(pentafluorophenyl)-porphyrinatozinc(n) 115 (Scheme 16).10... 

Blais et al. prepared tri- and tetra-meta-glucosylated chlorin derivatives.77 The aim was to assess how the sugar units linked to chlorin derivatives affect the photoactivity, cell internalization and subcellular localization in HT29 human adenocarcinoma cells. This was compared with the action due to meso-tetrakis(m-hydroxyphenyl)chlorin, a compound being formulated as photosensitiser (Foscan ) for palliative treatment of head and neck cancers. 

Fig. 10 Structures of dyes (a) 3,3 -di(3-sulfopropyl)-9-amino-thiacarbocyanine (dye 8), (b) 3,3 -di(3-sulfopropyl)-4,5,4, 5 -dibenzo-9-phcnyl-thiacarbocyanine (PTC), (c) meso-tetrakis(p-sulfo-natophenyl) porphine (TSPP, at pH lower than 4.8)...

Andrade SM, Costa SMB (2002) Aggregation kinetics of meso-tetrakis(4-sulfonatophenyl) porphine in the presence of proteins temperature and ionic strength effects. J Fluoresc 12 77-82... 

The water-soluble Fe porphyrin, 3Na+ [Fe(III)(TPPS)] -12H20 [H2TPPS4- = tetra-anionic form of meso-tetrakis(7r-sulfonatophenyl)porphine], has recently been shown to be an effective catalyst for the electroreduction of nitrite to ammonia [419]. The Fe meso-tetrakis(A -methyl-4-pyridyl) porphyrin and/or the Fe meso-tetrakis (jr -sulfophenyl) porphyrin complex shows a catalytic activity for the reduction of dioxygen in aqueous solutions, leading to hydrogen peroxide [420]. 

Fe model 1 (deoxy form) Fe(Tpiv)PP-(2-MeIm). The porphyrin ligand, Fe(Tpiv)PP, is the picket fence porphyrin, meso-tetrakis(a, a, a, a-o-pivalamidephenyl)porphyrin (Figure 16 of reference 9). In this chapter see Figure 7.9B. 

Figure 7.9 (A) Prevention of a-oxo dimer formation by distal-side porphyrin modifications. (Adapted with permission from the reference 19. Copyright 1985, Division of Chemical Edncation, Inc.) (B) Picket-fence porphyrin Fe(Tpjv)PP, meso-tetrakis(a, a, a, a-c>-pivalamidephenyl)porphyrin described in references 6,17,18, and 21.

P. Maillard, C. Huel, and M. Momenteau, Synthesis of new meso-tetrakis (glycosylated) porphyrins, Tetrahedron Lett. 33 8081 (1992). 

Iron(II) meso-tetrakis(2,4,6-trimethoxyphenyl)porphyrin and the triethoxy analogue have been synthesized by Vaska. These are different to the capped and picket fence porphyrins in that both sides of the porphyrin are sterically hindered. Dioxygen uptake by these iron(II) porphyrins at 25 °C in solution was found to be partially reversible. La Mar and co-workers166 have shown that the porphyrins Fe[T(2,4,6-OMe)3PP], Fe[T(2,4,6-OEt)3PP] and Fe[TpivPP] take up oxygen at low temperatures, in the absence of a base such as Melm or pyridine, to give dioxygen adducts of the... 

Groves et al. found that a simple heme-iodosobenzene system mimics the enzymic reactions.127 Cyclohexane and cyclohexene are oxidized to cyclohexanol and a mixture of cyclohexene oxide and cyclohexenol respectively by this system. Using meso-tetrakis-a,/J,a,/J-(o-acylamidophenyl)por-phinatoiron(III) chloride where the acyl group is (i )-2-phenylpropionyl or (S)-2 -methoxy-carbonyl-l,T-binaphthyl-2-carbonyl, optically active styrene oxides are obtained in 51% e.e. The Fe(TPP)Cl-PhIO system can also oxygenate arenes to arene oxides.128 Based on the following observations, mechanisms involving O—Felv(Por) t as the active species have been proposed (Scheme 30).127... 

The eclipsed tetra-BINAP porphyrin 171 was conveniently synthesized by condensation of the meso-tetrakis(2,6-dihydroxyphenyl)porphyrin 173 with the (S)-BINAP derivative 174 in the presence of K2C03. After removal of the staggered isomer iron was inserted by addition of Fe(CO)5/I2, and the resulting Fe(III)-complex 171 was used as a catalyst (0.2%) to epoxidize a series of six styrene derivatives in the presence of an excess of PhIO. In every case the corresponding (R)-epoxides were preferentially formed in yields up to 72%. The best ee-values were obtained for the electron deficient substrates 2-nitrostyrene (80% ee) and pentafluorostyrene (74% ee), [114],... 

For the synthesis of the porphyrin the formate ester of 3j3-hydroxy-5-cholenic acid 179 was coupled via amide bonds to the a,/ ,a,j -atropisomer of meso-tetrakis(o-aminophenyl)-porphyrin 170, using the mixed anhydride... 

Mn-TMPyP meso-Tetrakis(AI-methyl-pyridinium-4-yl)porphy-rinatomanganese (II) -pentaacetate... 

TMPyP meso-tetrakis(4-N-methyl-pyridiniumyl)porphyrin... 

Figure 2. C.-P.-K. model of energy minimized (MM-2, chem 3D) meso-tetrakis (p-methyl) phenyl porphyrin.

DiMagno, S.G., Williams, R.A. and Therien, M.J. (1994) Facile synthesis of meso-tetrakis(perfluoroalkyl) porphyrins spectroscopic properties and X-ray crystal structure of highly electron-deficient 5,10,15,20-tetrakis (heptafluoropropyl) porphyrin. J. Org. Chem., 59, 6943. 

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