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https://scholarbank.nus.edu.sg/handle/10635/90723
DC Field | Value | |
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dc.title | Spectral resolution of fluxional organometallics: Further observations and experimental results for Rh4(σ-CO)9(μ-CO)3 | |
dc.contributor.author | Allian, A.D. | |
dc.contributor.author | Garland, M. | |
dc.date.accessioned | 2014-10-09T07:08:25Z | |
dc.date.available | 2014-10-09T07:08:25Z | |
dc.date.issued | 2005 | |
dc.identifier.citation | Allian, 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.issn | 00657727 | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/90723 | |
dc.description.abstract | In-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.source | Scopus | |
dc.type | Conference Paper | |
dc.contributor.department | CHEMICAL & BIOMOLECULAR ENGINEERING | |
dc.description.sourcetitle | ACS National Meeting Book of Abstracts | |
dc.description.volume | 229 | |
dc.description.issue | 1 | |
dc.description.page | INOR-399 | |
dc.description.coden | ACSRA | |
dc.identifier.isiut | NOT_IN_WOS | |
Appears in Collections: | Staff Publications |
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