Jump to main content
Jump to site search

Issue 5, 2019
Previous Article Next Article

The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)5 (M = Fe, Ru, Os) complexes

Author affiliations

Abstract

The mechanisms for the photochemical CO-dissociation and the oxidative addition reactions are studied theoretically using three model systems: M(CO)5 (M = Fe, Ru, and Os) and the CASSCF/Def2-SVP (fourteen-electron/ten-orbital active space) and MP2-CAS/Def2-SVP//CASSCF/Def2-SVP methods. The structures of the intersystem crossings and the conical intersections, which play a decisive role in these CO photo-extrusion reactions, are determined. The intermediates and the transition structures in either the singlet or triplet states are also computed, in order to explain the reaction routes. These model studies suggest that after the irradiation of Fe(CO)5 with UV light, it quickly loses one CO molecule to generate a 16-electron iron tetracarbonyl, in either the singlet or the triplet states. It is found that the triplet Fe(CO)4 plays a vital role in the formation of the final oxidative addition product, Fe(CO)4(H)(SiMe3), but the singlet Fe(CO)4 plays a relatively minor role in the formation of the final product. However, its vacant coordination site interacts weakly with solvent molecules ((Me3)SiH) to yield the alkyl-solvated iron complexes, which are detectable experimentally. The theoretical observations show that Ru(CO)5 and Os(CO)5 have similar photochemical and thermal potential energy profiles. In particular, this study demonstrates that the oxidative addition yield for Fe is much greater than those for its Ru and Os counterparts, under the same chemical conditions.

Graphical abstract: The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)5 (M = Fe, Ru, Os) complexes

Back to tab navigation

Supplementary files

Article information


Submitted
14 Sep 2018
Accepted
07 Dec 2018
First published
21 Jan 2019

This article is Open Access

RSC Adv., 2019,9, 2626-2640
Article type
Paper

The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)5 (M = Fe, Ru, Os) complexes

Z. Zhang and M. Su, RSC Adv., 2019, 9, 2626
DOI: 10.1039/C8RA07669C

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