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
(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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https://lup.lub.lu.se/record/3187564
- author
- Hrovat, David A. ; Nordlander, Ebbe LU and Richmond, Michael G.
- organization
- publishing date
- 2012
- 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}}, }