DUGiDocsThe 'innocent' role of Sc3+ on a non-heme Fe catalyst in an O2 environment
Texto Completo
innocentRoleSc3.pdf
Solicita copia
Al rellenar este formulario estáis solicitando una copia del artículo, depositado en el repositorio institucional (DUGiDocs), a su autor o al autor principal del artículo. Será el mismo autor quien decidirá enviar una copia del documento a quien lo solicite si lo considera oportuno. En todo caso, la Biblioteca de la UdG no interviene en este proceso ya que no está autorizada a facilitar artículos cuando éstos son de acceso restringido.
Compartir
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
Tots els drets reservats