Jump to main content
Jump to site search

Issue 22, 2018
Previous Article Next Article

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

Author affiliations

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 methylperoxo product and others reverting to the reactants, and the validity of some of these paths has been confirmed by additional experiments. The balance between the barriers towards productive and unproductive paths reproduces the diverging experimental behavior of similar complexes and provides a general mechanistic picture for these processes.

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

Back to tab navigation

Supplementary files

Article information


Submitted
12 Mar 2018
Accepted
03 May 2018
First published
04 May 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 5039-5046
Article type
Edge Article

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

V. M. Fernández-Alvarez, S. K. Y. Ho, G. J. P. Britovsek and F. Maseras, Chem. Sci., 2018, 9, 5039
DOI: 10.1039/C8SC01161C

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements