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DFT Investigation o...
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
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Hrovat, David A. (author)
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- Nordlander, Ebbe (author)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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Richmond, Michael G. (author)
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(creator_code:org_t)
- 2012-09-05
- 2012
- English.
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In: Organometallics. - : American Chemical Society (ACS). - 1520-6041 .- 0276-7333. ; 31:18, s. 6608-6613
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http://dx.doi.org/10...
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Abstract
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- 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.
Subject headings
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
Publication and Content Type
- art (subject category)
- ref (subject category)
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