Tetraphenylporphinato iron

It was shown that dibenzothiophene oxide 17 is inert to 1-benzyl-l,4-dihydro nicotinamide (BNAH) but that, in the presence of catalytic amounts of metalloporphyrin, 17 is reduced quantitatively by BNAH. From experimental results with different catalysts [meso-tetraphenylporphinato iron(III) chloride (TPPFeCl) being the best] and a series of substituted sulfoxides, Oae and coworkers80 suggest an initial SET from BNAH to Fe1 followed by a second SET from the catalyst to the sulfoxide. The results are also consistent with an initial coordination of the substrate to Fem, thus weakening the sulfur-oxygen bond in a way reminiscent of the reduction of sulfoxides with sodium borohydride in the presence of catalytic amounts of cobalt chloride81. 

Applications of the core shielding factors in X-ray studies of pyrite, Fe(Il) phthalocyanine, and bis(pyridine)(meso-tetraphenylporphinato)iron(II) generally improve agreement with spectroscopic values (Su and Coppens 1996). 

Bis(tetrahydrofurane)(meso-tetraphenylporphinato)iron(II) (bTHF FeTPP) is the only known six-coordinate high-spin Fe(II) complex. Its THF ligands are rather loosely bound. Crystals slowly lose THF when exposed to the atmosphere, while the iron is five-coordinate in a solution in benzene (Reed et al. 1980). The magnetic susceptibilty of bTHF FeTPP is temperature dependent (Lecomte et al. 1986) and the axial Fe—O bonds shrink on cooling from 1.35 A at ambient temperature to 1.29 A at nitrogen temperature. 

Bis(pyridine)(meso-tetraphenylporphinato)iron(II), discussed in section 10.5.2, was reanalyzed to evaluate the importance of anharmonic motion in nitrogen-temperature transition metal studies. A number of different refinements are summarized in Table 10.13. It is striking that treating the Fe atom as spherical... 

Concerted One-Electron Reductions. Reduction of 02 in the presence of excess zinc cation [Znu(bpy)2+], (tetraphenylporphinato)iron(III) ion [(H20)+FemTPP], and cuprous ion [Cu MeCN)/] results in formation of metal-dioxygen adducts. Figures 9.13 and 9.14 illustrate the cyclic voltam-mograms for (FemTPP)Cl and tCuI(MeCN)4]C104, respectively, in the absence and presence of 02. Reaction schemes for the three metal-02 systems are outlined ... 

Lee WA, Yuan LC, Bruice TC (1988) Oxygen transfer from percarboxylic acids and alkyl hydroperoxides to (meso-tetraphenylporphinato)iron(III) and -chromium(III). J Am Chem Soc 110 4277 1283... 

Figure 1a. Perspective drawing of bis(pyridine)-(meso-tetraphenylporphinato)iron(II).

Peng SM, Ibers JA (1976) Stereochemistry of carbonylmetalloporphyrins - structure of (pyri-dine)(carbonyl)(5,10,15,20-tetraphenylporphinato)Iron(Ii). J Am Chem Soc 98 8032-8036... 

Almarsson, O., Bruice, T. C. (1995). A homolytic mechanism of 0-0 bond scission prevails in the reactions of alkyl hydroperoxides with an octacationic tetraphenylporphinato-iron(III) complex in aqueous solution, J. Am. Chem. Soc., 117 4533. 

Kadish, K.M. and R.K. Rhodes (1983). Thin-layer spectroelectrochemical evidence of anion binding to (tetraphenylporphinato)iron(II) in nonaqueous media. Inorg. Chem. 22, 1090-1094. 

CftAH28FeN7 0.5 C5H5N, Azido(pyridine)(tetraphenylporphinato)iron-(III) pyridine solvate, 45B, 536 Ci,aH28NaPd, Palladium( 11) tetraphenylporphine, 29, 617 C44H29Ago 5N4, (Tetraphenylporphine)silver-tetraphenylporphine, 38B, 508... 

C4 sHa aClFeNijOa f Perchlorato (m-tetraphenylporphinato) iron (111) hemi-m-xylene solvate, 45B, 538... 

The majority of photooxidation reactions carried out with metalloporphyrins can be classified as atom transfer types. Under thermal conditions such reactions are exemplified by the oxidation reactions that can be carried out with cytochrome P-450. Upon photolysis the //-oxo-bis(tetraphenylporphinato)iron(III) complex (FeTPP)20 undergoes disproportionation to give the Fe(II) complex FeTPP, and the Fe(rV) complex Fe(0)TPP (Ref. 49) ... 

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