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Title: Bimetallic catalytic binuclear elimination reaction. Experimental, spectroscopic and kinetic elucidation
Keywords: Catalytic binuclear elimination, Homogeneous, Hydroformylation, In-situ FTIR, Rhodium, Synergism
Issue Date: 9-Feb-2004
Source: LI CHUANZHAO (2004-02-09). Bimetallic catalytic binuclear elimination reaction. Experimental, spectroscopic and kinetic elucidation. ScholarBank@NUS Repository.
Abstract: The bimetallic origins of catalytic synergism were studied using Rh4(CO)12/HMn(CO)5 catalyzed hydroformylation of 3,3-dimethylbut-1-ene, Rh4(CO)12/HMn(CO)5 catalyzed hydroformylation of cyclopentene, and Rh4(CO)12/HRe(CO)5 catalyzed hydroformylation of cyclopentene. A dramatic increase in the catalytic rate was observed when both metals were used simultaneously. Detailed in-situ FTIR measurements indicated the observable presence of only homometallic complexes during catalysis in Rh/Mn bimetallic catalyzed hydroformylation reactions, while a dinuclear complex RhRe(CO)9 was observed in the Rh/Re bimetallic catalyzed hydroformylation. The kinetics of product formation shows a distinct linear-bilinear form in observables. The linear term represents the classic unicyclic rhodium catalysis while the bilinear term indicates a hydride attack on an acyl species. These spectroscopic and kinetic results strongly suggest that the origin of synergism is the presence of bimetallic catalytic binuclear elimination. This appears to be the first detailed evidence for such a catalytic mechanism and its implications for selectivity and non-linear catalytic activity are accordingly discussed.
Appears in Collections:Ph.D Theses (Open)

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