Mechanistic insights into the allylic oxidation of aliphatic compounds by tetraamido iron(v) species: A C–H vs. O–H bond activation

Abstract

The main challenges in synthetic organic chemistry are chemoselective oxidation of C-H bond by natural complexes under mild conditions. Heme and non-heme metal complexes with several oxidants such as dioxygen,...

Effect of the ring size of TMC ligands in controlling C–H bond activation by metal-superoxo species

“…In our previous studies, we performed a method assessment using functionals such as B3LYP, 14 B3LYPD-2, 15 wB97XD, 16 B97D, 15 M06-2X, 17 TPPSh, 18 and MP2 19 and it was found that the B3LYP, B3LYP-D2 and wB97XD functionals predict the correct spin state of transition metal complexes. 10 m ,20 Furthermore, among them, B3LYP-D2 was found to be superior. Thus, we restricted our calculations to the B3LYP-D2 functional.…”

Theoretical insights for generation of terminal metal-oxo species and involvement of the “oxo wall”

“…S1 and Table S2 of ESI †). 14 S4 of ESI †). Upon moving rightwards in the Periodic Table from Cr to Mn and Fe, one and two extra electrons are added into the d orbital, respectively, whereas the pairing of electrons takes place in Co, Ni, and Cu species.…”

“…S1 and Table S2 of ESI†). 14 Spin natural orbital (SNO) analysis showed the transfer of an electron to the metal d orbital (Fig. S4 of ESI†).…”

Theoretical study of the formation of metal–oxo species of the first transition series with the ligand 14-TMC: driving factors of the “Oxo Wall”

“…Based on earlier theoretical and experimental studies, a mechanism for the generation of metal(IV)-oxo and metal(V)oxo species from metal(III)-hydroperoxo species is shown in Scheme S1 of the ESI. † 5,66,[90][91][92][93] This mechanism is based on O⋯O bond cleavage, either homolytic or heterolytic. Homolytic cleavage gives the metal(IV)-oxo species and the heterolytic cleavage gives metal(V)-oxo species along with OH • / OH − , respectively.…”

“…Based on earlier theoretical and experimental studies, a mechanism for the generation of metal( iv )–oxo and metal( v )–oxo species from metal( iii )-hydroperoxo species is shown in Scheme S1 of the ESI † 5,66,90–93 . This mechanism is based on O⋯O bond cleavage, either homolytic or heterolytic.…”