The "innocent" role of Sc3+ on a non-heme Fe catalyst in an O2 environment
KAUST DepartmentKAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
MetadataShow full item record
AbstractDensity 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. This journal is © the Partner Organisations 2014.
SponsorsA.P. thanks the Spanish MIClNN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). We thank Prof. Lawrence Que Jr for helpful comments.
PublisherRoyal Society of Chemistry (RSC)