Porphyrin-ketones

Papkovsky D.B., Ponomarev G.V., Trettnak W., Oleary P., Phosphorescent Complexes of Porphyrin Ketones - Optical Properties And Application to Oxygen Sensing, Anal. 

Hartmann P., Trettnak W., Effects of polymer matrices on calibration functions of luminescent oxygen sensors based on porphyrin ketone complexes, Anal. Chem. 1996 68(15) 2615-2620. 

Figure 19.14. Absorption indenusaon spectra (rfaj iospbofesceot porphyrin ketone derivative. Revised fiott Ret 40.

P kovsky. D. B.. Ponomarev. G. V.. Trettnak, W.. and O Leary. P. 1995. Phoqiborescent complexes of porphyrin ketones Optical properties and applications to oxygen sensing. Anat Chem. 67 4112-4117. 

Paty4pnriine, 373 POPOP.3,5 645,649 Porphyrin ketone derivative, 539 I itassi urn-binding beozoferan isophtbalate (PBFI),16.17,554.555.556... 

Thallium(III) acetate reacts with alkenes to give 1,2-diol derivatives (see p. 128) while thallium(III) nitrate leads mostly to rearranged carbonyl compounds via organothallium compounds (E.C. Taylor, 1970, 1976 R.J. Ouelette, 1973 W. Rotermund, 1975 R. Criegee, 1979). Very useful reactions in complex syntheses have been those with olefins and ketones (see p. 136) containing conjugated aromatic substituents, e.g. porphyrins (G. W. Kenner, 1973 K.M. Smith, 1975). 

The X-ray structures are known of a number of ketone ligands, including hexanedione and 4-methylcyclohexanone, that have bound as monodentate ligands in the fifth coordination site of zinc porphyrin complexes.347,348 Oxaphlorin dimeric compounds are also known where the oxygen from a neighboring porphyrin ring coordinates in the fifth coordination site of a neighboring zinc porphyrin unit.349... 

Porphyrins and Plant Pigments Chiorophyii Hemin Carotenes and Xanthophyiis > Chlorin Phaeophytin hydrocarbons Phytane, pristane, carotenoids, isoprenoids, alcohols, ketones, acids, porphyrins... 

An electron-deficient manganese(III) porphyrin complex was reported to catalyze the oxidation of alkanes by PhI(OAc)2 in mixed [BMIM]PF6/CH2Cl2 at room temperature (230). Cyclic alkanes were oxidized to secondary alcohols and ketone. A highly active and short-lived intermediate, Mn = O, was observed in the ionic liquid, whereas in CH2CI2 the same reaction gave only a less-active intermediate, Mn " = O. 

In a recent example metalloporphyrins are used as the sensing dyes for a wide variety of odorants, including alcohols, amines, arenes, ethers, halocarbons, ketones, phosphines, thioethers and thiols. An array of four different metalloporphyrins are placed on a substrate and exposed to the vapours for 30 s. The various vapour molecules coordinate onto the central metal atoms of the porphyrins, causing them to change colour and producing a unique four-colour array. The resulting colour array is compared with a library of known chemicals or mixtures and identification is achieved. 

Although the cofacial diporphyrins represent a vibrant and innovative direction in dioxygen activation, simple porphyrins and their derivatives also remain an important research area. The dichlorophenyl-substituted porphyrin tdcpp [5,10,15,20-tetrakis(2,6-dichlorophenyl)-porphyrin] forms a complex with cobalt(II), [Co(tdcpp)], and catalyzes the oxidation of conjugated olefins to (after experimental workup) ketones in the presence of dioxygen and triethylsilane (80) a hydroperoxide intermediate has been isolated from these reactions (81). 

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