Jump to main content
Jump to site search

Issue 5, 2018
Previous Article Next Article

How to tame a palladium terminal oxo

Author affiliations

Abstract

The isolation of terminal oxo complexes of the late transition metals promises new avenues in oxidation catalysis like the selective and catalytic hydroxylation of unreactive CH bonds, the activation of water, or the upgrading of olefins. While terminal oxo ligands are ubiquitous for early transition metals, well-characterized examples with group 10 metals remain hitherto elusive. In search for palladium terminal oxo complexes, the relative stability/reactivity of such compounds are evaluated computationally (CASSCF/NEVPT2; DFT). The calculations investigate only well-known ligand systems with established synthetic procedures and relevance for coordination chemistry and homogeneous catalysis. They delineate and quantify, which electronic properties of ancillary ligands are crucial for taming otherwise highly reactive terminal oxo intermediates. Notably, carbene ligands with both strong σ-donor and strong π-acceptor properties are best suited for the stabilization of palladium(II) terminal oxo complexes, whereas ligands with a weaker ligand field lead to highly reactive complexes. Strongly donating ligands are an excellent choice for high-valent palladium(IV) terminal oxo compounds. Low coordinate palladium(II) as well as high-valent palladium(IV) complexes are best suited for the activation of strong bonds.

Graphical abstract: How to tame a palladium terminal oxo

Back to tab navigation

Supplementary files

Article information


Submitted
23 Nov 2017
Accepted
04 Dec 2017
First published
13 Dec 2017

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, 1155-1167
Article type
Edge Article

How to tame a palladium terminal oxo

D. Munz, Chem. Sci., 2018, 9, 1155
DOI: 10.1039/C7SC05034H

This article is licensed under a Creative Commons Attribution 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.

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