Rare earth porphyrinates

Analogies of Rare Earth Porphyrin Doubledeckers with the Special Pair of Bacteriochlorophylls in Bacterial Photosynthesis... 

Paramagnetic rare-earth porphyrins, TPPErOH (TPP 5,10,15,20-tetraphenylporphin) and TPPEr(dpm) (dpm 2,2,6,6-tetramethyl-3,5-heptanedionate), emit not only but also S2 fluorescence even if a sequence of the... 

Rare earth bisporphyrinates, optical spectra, 94-104 Rare earth porphyrins—See Metalloporphyrins Rate constants... 

Gaiduk, M. I., Grigoryants, V. V., Mironov, A. R, Chissov, V. I., Rumyantseva, V. D. Sukhin, G. M. (1990). Fiber-laser IR luminescence diagnostics of malignant tumors using rare-earth porphyrins. J. Photochem. Photobiol, B Biology, 7(1), 15-20. 

Although the copolymerization of propylene oxide with C02 takes place effectively with organozinc additives or the (tetraphenyl) porphyrin-AlCl system [61], the copolymerization of epichlorohydrin with C02 seldom occurs with these catalysts. Shen et al. [62] showed that a rare earth metal catalyst such as the Nd(2-EP)3/AliBu3 (Al/Nd = 8) system was very effective for the copolymerization of epichlorohydrin with C02 (30-40 atm) at 60 °C (Scheme 16). The content of C02 in the copolymer reached 23-24 mol % when 1,4-dioxane was used as solvent. 

A review has appeared on the synthesis of enantiomerically enriched aziridines by the addition of nitrenes to alkenes and of carbenes to imines.45 A study of the metal-catalysed aziridination of imines by ethyl diazoacetate found that mam group complexes, early and late transition metal complexes, and rare-earth metal complexes can catalyse the reaction.46 The proposed mechanism did not involve carbene intermediates, the role of the metal being as a Lewis acid to complex the imine lone pah. Ruthenium porphyrins were found to be efficient catalysts for the cyclopropana-tion of styrenes 47 High diastereoselectivities in favour of the //-product were seen but the use of chiral porphyrins gave only low ees. 

Rare Earth Complexes with Porphyrin Type Ligands... 

Except for the homoleptic bi(porphyrinato) and tri(porphyrinato) rare earth complexes, complexes with different porphyrin macrocycles were also investigated. To date, some sandwich type heteroleptic bis(porphyrinato) rare earth double-deckers have been synthesized. However, few have been structurally characterized via single crystal X-ray diffraction analysis [47]. Among these, Ce(IV)(OEP)(TPP) is the only structurally characterized neutral heteroleptic bis(porphyrinato) rare earth double-decker complex [48]. Using an improved short route, Coutsolelos and coworkers prepared and isolated a series of heteroleptic bis(porphyrinato)... 

The first monomeric porphyrinato rare earth complex was reported in 1974 [49]. However, only a few reports on these systems have appeared in the literature since then. In 1991, Schaverien and Orpent reported the synthesis of the monomeric porphyrinato lutetium complex Lu(OEP)[CH(Si(CH3)2] from the reaction between Lu CH[Si(CH3)3]2 3 and H2OEP in toluene [50]. Eigure 4.33 displays its molecular structure. The complex belongs to the monoclinic system and crystallizes in a space group P2 lc with a = 1.4879(6) nm, 7 = 2.0644(10) nm, c= 1.4161(5) nm, P= 96.38(3)°, V = 4.323(3) nm, andZ = 4. The coordination geometry can be described as square-pyramidal. In the crystal, the porphyrin... 

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