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DFT Investigation of the Mechanism of Phosphine-Thioether Isomerization in the Triosmium Cluster Os-3(CO)(10)(Ph2PCH2CH2SMe): Migratory Preference for the Formation of an Edge-Bridged Thioether versus a Phosphine Moiety

Hrovat, David A. ; Nordlander, Ebbe LU and Richmond, Michael G. (2012) In Organometallics 31(18). p.6608-6613
Abstract
The rearrangement of the phosphine-thioether ligand in 1,2-(P-eq,S-eq)-Os-3(CO)(10)(Ph2PCH2CH2SMe) to 1,1-(P-eq,S-ax)-Os-3(CO)(10)(Ph2PCH2CH2SMe) was investigated by electronic structure calculations. The chelated isomer lies 2.5 kcal/mol lower in energy than its bridged counterpart, and the barrier computed for the mechanism is in agreement with the results from our earlier experimental study. Phosphine-thioether isomerization occurs via three distinct steps that involve the migration of the CO and SMe groups in a plane that is perpendicular to the trimetallic core. One of the intermediates on the reaction surface corresponds to the 50e cluster Os-3(CO)(9)(mu-CO)(mu-Ph2PCH2CH2SMe), whose edge-bridging thioether moiety functions as a 4e... (More)
The rearrangement of the phosphine-thioether ligand in 1,2-(P-eq,S-eq)-Os-3(CO)(10)(Ph2PCH2CH2SMe) to 1,1-(P-eq,S-ax)-Os-3(CO)(10)(Ph2PCH2CH2SMe) was investigated by electronic structure calculations. The chelated isomer lies 2.5 kcal/mol lower in energy than its bridged counterpart, and the barrier computed for the mechanism is in agreement with the results from our earlier experimental study. Phosphine-thioether isomerization occurs via three distinct steps that involve the migration of the CO and SMe groups in a plane that is perpendicular to the trimetallic core. One of the intermediates on the reaction surface corresponds to the 50e cluster Os-3(CO)(9)(mu-CO)(mu-Ph2PCH2CH2SMe), whose edge-bridging thioether moiety functions as a 4e donor ligand. Alternative mechanisms involving ligand dissociation/association and merry-go-round sequences are energetically prohibitive. (Less)
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author
; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
31
issue
18
pages
6608 - 6613
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000309022700014
  • scopus:84866718355
ISSN
1520-6041
DOI
10.1021/om300640t
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
id
b050b522-c420-46a4-8bd0-aa7135dc016b (old id 3187564)
date added to LUP
2016-04-01 10:04:06
date last changed
2022-04-27 18:14:03
@article{b050b522-c420-46a4-8bd0-aa7135dc016b,
  abstract     = {{The rearrangement of the phosphine-thioether ligand in 1,2-(P-eq,S-eq)-Os-3(CO)(10)(Ph2PCH2CH2SMe) to 1,1-(P-eq,S-ax)-Os-3(CO)(10)(Ph2PCH2CH2SMe) was investigated by electronic structure calculations. The chelated isomer lies 2.5 kcal/mol lower in energy than its bridged counterpart, and the barrier computed for the mechanism is in agreement with the results from our earlier experimental study. Phosphine-thioether isomerization occurs via three distinct steps that involve the migration of the CO and SMe groups in a plane that is perpendicular to the trimetallic core. One of the intermediates on the reaction surface corresponds to the 50e cluster Os-3(CO)(9)(mu-CO)(mu-Ph2PCH2CH2SMe), whose edge-bridging thioether moiety functions as a 4e donor ligand. Alternative mechanisms involving ligand dissociation/association and merry-go-round sequences are energetically prohibitive.}},
  author       = {{Hrovat, David A. and Nordlander, Ebbe and Richmond, Michael G.}},
  issn         = {{1520-6041}},
  language     = {{eng}},
  number       = {{18}},
  pages        = {{6608--6613}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Organometallics}},
  title        = {{DFT Investigation of the Mechanism of Phosphine-Thioether Isomerization in the Triosmium Cluster Os-3(CO)(10)(Ph2PCH2CH2SMe): Migratory Preference for the Formation of an Edge-Bridged Thioether versus a Phosphine Moiety}},
  url          = {{http://dx.doi.org/10.1021/om300640t}},
  doi          = {{10.1021/om300640t}},
  volume       = {{31}},
  year         = {{2012}},
}