Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja073339v
Title: Synchronicity of mononuclear and dinuclear events in homogeneous catalysis. Hydroformylation of cyclopentene using Rh 4(CO) 12 and HRe(CO) 5 as precursors
Authors: Li, C.
Chen, L. 
Garland, M. 
Issue Date: 31-Oct-2007
Citation: Li, C., Chen, L., Garland, M. (2007-10-31). Synchronicity of mononuclear and dinuclear events in homogeneous catalysis. Hydroformylation of cyclopentene using Rh 4(CO) 12 and HRe(CO) 5 as precursors. Journal of the American Chemical Society 129 (43) : 13327-13334. ScholarBank@NUS Repository. https://doi.org/10.1021/ja073339v
Abstract: The combined application of two or more metals in homogeneous catalysis can lead to synergistic effects; however, the phenomenological basis for these observations often goes undetermined. The heterobimetallic catalytic binuclear elimination reaction, a system involving both mononuclear and dinuclear intermediates, has been repeatedly suggested as a possible mechanism. In the present contribution, the simultaneous application of Rh 4(CO) 12 and HRe(CO) 5 as precursors in the hydroformylation reaction leads to a very strong synergistic rate effect. In situ spectroscopic measurements confirm the presence of both mononuclear and dinuclear intermediates such as RCORh(CO) 4 and RhRe(CO) 9 in the active system. Moreover, kinetic analysis confirms interconversion of these intermediates as well as their statistical correlation with organic product formation. Specifically, the rate of hydrogen activation by RhRe(CO) 9 is exactly equal to the rate of aldehyde formation from binuclear elimination between HRe(CO) 5 and RCORh-(CO) 4 at all reaction conditions studied. Thus the catalytic events involving mononuclear species and those involving dinuclear species are synchronized. In the present experiments, the new topology is orders of magnitude more efficient than the corresponding unicyclic rhodium system. © 2007 American Chemical Society.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/90248
ISSN: 00027863
DOI: 10.1021/ja073339v
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