title: The "innocent" role of Sc(3+) on a non-heme Fe catalyst in an O2 environment.
abstract: 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 [Fe(II)(TMC)](2+) (R) and O2 in the presence of acid H(+) and reductant BPh4(-). We also addressed the possible role of redox-inactive Sc(3+) 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 Sc(3+)-peroxo-Fe(3+) 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.
authors.affiliation: Institut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, Campus de Montilivi, E-17071 Girona, Catalonia, Spain. albert.poater@udg.edu.
authors.forename: Albert
authors.initials: A
authors.lastname: Poater
authors.forename: Sai Vikrama
authors.initials: SV
authors.lastname: Chaitanya Vummaleti
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
mesh_terms: D002384:Catalysis; D019295:Computational Biology; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D012538:Scandium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D005296:Ferrous Compounds; D009942:Organometallic Compounds; D010100:Oxygen; D012538:Scandium