The key intermediate in the amination of saturated C-H bonds: synthesis, X-ray characterization and catalytic activity of Ru(TPP)(NAr)(2) (Ar = 3,5-(CF(3))(2)C(6)H(3)).

The complex Ru(TPP)(NAr)(2) inserts a nitrene group into allylic and benzylic C-H bonds and is the key intermediate in the ruthenium porphyrin-catalyzed amination of hydrocarbons by aryl azides.

Nitrene transfer reactions mediated by metallo-porphyrin complexes.

Nitrene transfer reactions represent a useful methodology to synthesize in a few steps high added-value compounds used as organic intermediates. Herein, we describe the catalytic activity of metal porphyrin complexes in a wide range of reactions such as C-H hydrocarbon amination and olefin aziridination to synthesize nitrogen containing molecules. All the most important nitrene sources have been reviewed stressing the potentiality and limits of each one in the particular class of chemical transformation.

Rearrangement of N-aryl-2-vinylaziridines to benzoazepines and dihydropyrroles: a synthetic and theoretical study.

Herein we report the one-pot synthesis of several N-heterocyclic compounds by rearrangement reactions of N-aryl-2-vinylaziridines. The optimization of the synthetic methodology employed allowed us to obtain differently substituted 2,5-dihydro-1H-benzo[b]azepines in good yields and purities. The relationship between the nature of the starting N-aryl-2-vinylaziridine and the obtained N-heterocycle was also investigated.

Structural determination of ruthenium-porphyrin complexes relevant to catalytic epoxidation of olefins.

A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis.