Determining the pure component spectra of trace organometallic intermediates by combined application of in situ Raman spectroscopy and band-target entropy minimization analysis |
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| Institution: | 1. Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia;2. Department of Physical and Organic Chemistry, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia;3. Jožef Stefan International Postgraduate School, Jamova 39, 1000 Ljubljana, Slovenia;1. Department of Chemical Engineering, University of Environment, P.O. Box 31746-118, Karaj, Iran;2. Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran, Iran;3. Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran;4. Department of Chemical Engineering, Science and Technology, University of Mazandaran, Behshahr, Iran;1. Department of Industrial Engineering, Faculty of Engineering, Kharazmi University, Tehran, Iran;2. Department of Industrial Engineering, Sharif University of Technology, Tehran, Iran;3. School of Engineering and Sciences, Tecnológico de Monterrey, E. Garza Sada 2501 Sur, C.P. 64849, Monterrey, Nuevo León, Mexico;1. Key Laboratory for Embedded and Network Computing of Hunan Province, School of information science and engineering, Hunan University, 410082 Changsha, China;2. Department of Computer Science, University of Regina, Regina, Saskatchewan, Canada;1. Department of Pharmacy, Health and Nutritional Sciences, University of Calabria, Via P. Bucci, Rende, CS 87036, Italy;2. Department of Environmental Chemistry, IDAEA-CSIC, C/Jordi Girona, 18-26, Barcelona 08034, Spain |
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| Abstract: | Trace organometallic intermediates arising from complex organic syntheses are usually quite difficult to detect spectroscopically. In situ FTIR and in situ NMR are the only techniques that are used with any regularity for such studies. In this contribution, high-pressure in situ Raman spectroscopic measurements were performed for the rhodium catalyzed hydroformylation of 3,3-dimethylbut-1-ene using Rh4(CO)12 as catalyst precursor at 298 K – a reaction extensively studied previously by more sensitive in situ FTIR. The Raman spectroscopic measurements were analyzed using the band-target entropy minimization (BTEM) algorithm. As expected, the pure component spectra of dissolved CO, 3,3-dimethylbut-1-ene, and 4,4-dimethylpentanal were easily recovered. In addition, the pure component spectra of the precursor Rh4(CO)12 and the intermediate RCORh(CO)4 (R = (CH3)3CCH2CH2 ) were successfully reconstructed – even though the mean concentrations of both species were on the order of 150 ppm. The BTEM estimate of the Raman spectrum of RCORh(CO)4 is reported for the first time. This Raman spectrum is consistent with the DFT predicted spectrum. This study represents the first combined application of Raman spectroscopy and BTEM analysis to a homogeneously catalyzed metal-mediated reaction. The potential and limitations of this general approach are discussed. |
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| Keywords: | Intermediates Organometallics In situ Raman spectroscopy BTEM DFT Spectral reconstruction |
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