Ítem


The ’innocent’ role of Sc3+ on a non-heme Fe catalyst in an O2 environment

Density functional theory calculations have been used to investigate the reaction mechanism proposed for the formation of an oxoiron(iv) complex [Fe IV(TMC)O]2+ (P) (TMC = 1,4,8,11-tetramethylcyclam) starting from a non-heme reactant complex [FeII(TMC)]2+ (R) and O2 in the presence of acid H+ and reductant BPh4 -. We also addressed the possible role of redox-inactive Sc3+ as a replacement for H+ acid in this reaction to trigger the formation of P. Our computational results substantially confirm the proposed mechanism and, more importantly, support that Sc 3+ could trigger the O2 activation, mainly dictated by the availability of two electrons from BPh4 -, by forming a thermodynamically stable Sc3+-peroxo-Fe3+ core that facilitates O-O bond cleavage to generate P by reducing the energy barrier. These insights may pave the way to improve the catalytic reactivity of metal-oxo complexes in O2 activation at non-heme centers

Royal Society of Chemistry (RSC)

Director: Ministerio de Ciencia e Innovación (Espanya)
Autor: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi
Resum: Density functional theory calculations have been used to investigate the reaction mechanism proposed for the formation of an oxoiron(iv) complex [Fe IV(TMC)O]2+ (P) (TMC = 1,4,8,11-tetramethylcyclam) starting from a non-heme reactant complex [FeII(TMC)]2+ (R) and O2 in the presence of acid H+ and reductant BPh4 -. We also addressed the possible role of redox-inactive Sc3+ as a replacement for H+ acid in this reaction to trigger the formation of P. Our computational results substantially confirm the proposed mechanism and, more importantly, support that Sc 3+ could trigger the O2 activation, mainly dictated by the availability of two electrons from BPh4 -, by forming a thermodynamically stable Sc3+-peroxo-Fe3+ core that facilitates O-O bond cleavage to generate P by reducing the energy barrier. These insights may pave the way to improve the catalytic reactivity of metal-oxo complexes in O2 activation at non-heme centers
Accés al document: http://hdl.handle.net/2072/295631
Llenguatge: eng
Editor: Royal Society of Chemistry (RSC)
Drets: Tots els drets reservats
Matèria: Catalitzadors
Catalysts
Funcional de densitat, Teoria del
Density functionals
Títol: The ’innocent’ role of Sc3+ on a non-heme Fe catalyst in an O2 environment
Tipus: info:eu-repo/semantics/article
Repositori: Recercat

Matèries

Autors