Reactivity of Rare Earth Metal Porphyrins/Phthalocyanines in Acid Media

Porphyrinoid actinide complexes

“…Intense bands at 426 and 462 nm were also seen for 35 and 36 , respectively, that were attributed to a porphyrin-to-actinide( iii ) charge-transfer transitions. 29,61 In contrast, the broad absorption bands beyond 650 nm were ascribed to resonance interactions involving the porphyrin ligands. 29…”

“…29,61 In contrast, the broad absorption bands beyond 650 nm were ascribed to resonance interactions involving the porphyrin ligands. 29…”

“…The triple-decker tetraphenylporphyrin complexes 35 and 36 , assigned as being thorium( iii ) 60 and uranium( iii ) 61 species, respectively, by Lomova and co-workers are, apparently, the only examples of triple-decker actinide complexes based on porphyrinoids. 29 The double and triple-decker uranium porphyrin complexes were prepared by heating tetraphenyl porphyrin (H 2 TPP) and UO 2 (AcO) 2 in a 1 : 10 molar ratio in benzonitrile or phenol at reflux for 19 h (Fig. 17).…”

“…Double-decker americium complexes were reported by Moskalev and co-workers; these species were obtained by the reaction of americium acetate with o-phthalonitrile followed by electrocrystallization from a dimethylformamide-hydrazine hydrate mixture. 29,30 It was suggested that the americium complex existed as [AmPc 2 ] À1 . However, an X-ray diffraction analysis of the crystalline powder led to the conclusion that the americium in the presumed sandwich complex (5) was in the tervalent state, i.e., [Am III Pc 2 ] 0 , in which the americium(III) centre is located between two phthalocyanine macrocycles with one acting as formal À2 charge and the other acting as formal À1 charge within each molecule (Fig.…”

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

“…Most typical complexing ions form stable porphyrin complexes, the oxidation state in which can change from +1 to +6. [1][2][3] The rate constant of the metal porphyrins (MPs) dissociation into a metal cation and a porphyrin ligand was recognized as the best characteristic of the MP stability beginning from the first works in the topic to the recent ones [4][5][6][7][8][9] due to irreversibility of the MP formation and dissociation reactions. According to this frame of reference, main group porphyrin complexes should be attributed to the most stable MPs despite the fact that the 13, 14, 15 group p-elements are located in the Periodic Table between the ionic and covalent compounds that the elements form.…”