Please use this identifier to cite or link to this item: https://scholarbank.nus.edu.sg/handle/10635/90723
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dc.titleSpectral resolution of fluxional organometallics: Further observations and experimental results for Rh4(σ-CO)9(μ-CO)3
dc.contributor.authorAllian, A.D.
dc.contributor.authorGarland, M.
dc.date.accessioned2014-10-09T07:08:25Z
dc.date.available2014-10-09T07:08:25Z
dc.date.issued2005
dc.identifier.citationAllian, A.D.,Garland, M. (2005). Spectral resolution of fluxional organometallics: Further observations and experimental results for Rh4(σ-CO)9(μ-CO)3. ACS National Meeting Book of Abstracts 229 (1) : INOR-399. ScholarBank@NUS Repository.
dc.identifier.issn00657727
dc.identifier.urihttp://scholarbank.nus.edu.sg/handle/10635/90723
dc.description.abstractIn-situ FTIR spectroscopy at 1 cm resolution was conducted on n-hexane solutions of Rh4(σ-CO)9(μ-CO)3 on the interval T = 268-288 K and PT = 0.1-7.0 MPa using either helium or CO as dissolved gas. A new spectral pattern was recovered with terminal vibrations at 2075, 2069.8, 2044.6 and 2042/cm. The new spectrum indicated the presence of either one all terminal structure Rh4(σ-CO)12, or the co-existence of two highly symmetric terminal geometries with similar free energies. The equilibrium between Rh4(σ-CO)12 and Rh4(σ-CO)9(μ-CO)3 was determined in the presence of both helium and CO. The equilibrium constant Keq = [Rh4(σ-CO)12]/[Rh4 (σ-CO)9(μ-CO)3 at 275 K was circa 0.011. The free energy indicated a very small difference between the bridged and terminal geometry, and the lower entropy was consistent with a higher symmetry. This study illustrated the considerable utility of qualitative IR spectroscopy (occurring on a fast vibrational timescale) combined with sophisticated deconvolution techniques to resolve systems which were fluxional on the NMR time scale. This is an abstract of a paper presented at the 229th ACS National Meeting (San Diego, CA 3/13-17/2005).
dc.sourceScopus
dc.typeConference Paper
dc.contributor.departmentCHEMICAL & BIOMOLECULAR ENGINEERING
dc.description.sourcetitleACS National Meeting Book of Abstracts
dc.description.volume229
dc.description.issue1
dc.description.pageINOR-399
dc.description.codenACSRA
dc.identifier.isiutNOT_IN_WOS
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