Comparative Study of the Catalytic Amination of Benzylic C-H Bonds Promoted by Ru(TPP)(py)2 and Ru(TPP)(CO)
Articolo
Data di Pubblicazione:
2015
Citazione:
Comparative Study of the Catalytic Amination of Benzylic C-H Bonds Promoted by Ru(TPP)(py)2 and Ru(TPP)(CO) / G. Manca, C. Mealli, D.M. Carminati, D. Intrieri, E. Gallo. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2015:29(2015), pp. 4885-4893. [10.1002/ejic.201500656]
Abstract:
A combined experimental and DFT-based theoretical analysis elucidated the influence of the axial ligand L on the catalytic activity of Ru(porphyrin)L complexes in promoting the amination of benzylic C-H bonds by organic azides (RN3). Experimental data indicated that the catalytic activity of Ru(TPP)(CO) (1) (TPP = dianion of tetraphenylporphyrin) is comparable to that of Ru(TPP)(py)2 (2) (py = pyridine). DFT modelling disclosed that 2 can be regarded as a precatalyst that becomes active after the endergonic loss of one pyridine ligand to give the unsaturated species [Ru](py) (11) [Ru] = Ru(porphine). This complex would react with RN3 to give the mono-imido singlet complex [Ru](py)(NR)S (6S), which can be easily transformed into the triplet isomer 6T having diradical character at the imido N atom. The subsequent formation of the benzylic amine PhCH2NHR occurs through a radical homolytic activation of one C-H bond of the toluene substrate (PhCH3). Conversely, by staying on the singlet potential-energy surface, 6S can undergo dissociation of the pyridine ligand to form [Ru](NR). This complex can activate another RN3 molecule to form the bis-imido compound [Ru](NR)2, which is also catalytically active. At this point, the mechanism becomes independent of the nature of the original ligand L coordinated to [Ru]. The catalytic activity of Ru(TPP)(py)2 (2) (TPP = dianion of tetraphenylporphyrin, py = pyridine) in the amination of C-H bonds by organic azides (RN3) was experimentally compared to that of Ru(TPP)(CO) (1). A computational analysis corroborates similar radical mechanisms with a triplet imido intermediate, in spite of the electronic differences of the apical ligands.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
Amination; Density functional calculations; Porphyrinoids; Reaction mechanisms; Ruthenium; Inorganic Chemistry
Elenco autori:
G. Manca, C. Mealli, D.M. Carminati, D. Intrieri, E. Gallo
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