A DFT-based mechanistic proposal for the light-driven insertion of dioxygen into Pt(ii)-C bonds.

ABSTRACT: The photocatalyzed insertion of dioxygen into the Pt(ii)-methyl bond in terpyridine platinum complexes has been shown to proceed efficiently, but its mechanism remains a challenge. In particular, there are serious counter-intuitive differences in the reactivity of structurally similar complexes. M06 calculations in solvent with a valence double-ζ basis set supplemented by polarization and diffusion shells (benchmarked against ωB97x-D calculations with a larger basis set) are able to provide a satisfactory mechanistic answer. The proposed mechanism starts with the absorption of a photon by the metal complex, which then evolves into a triplet state that reacts with the triplet dioxygen fragment. A variety of possible reaction paths have been identified, some leading to the meth

SUBMITTER: Fernandez-Alvarez VM 

PROVIDER: S-EPMC5994795 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature