Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja029499i
Title: The Rh4(CO)12-catalyzed hydroformylation of 3,3-dimethylbut-1-ene promoted with HMn(CO)5. Bimetallic catalytic binuclear elimination as an origin for synergism in homogeneous catalysis
Authors: Li, C.
Widjaja, E.
Garland, M. 
Issue Date: 7-May-2003
Citation: Li, C., Widjaja, E., Garland, M. (2003-05-07). The Rh4(CO)12-catalyzed hydroformylation of 3,3-dimethylbut-1-ene promoted with HMn(CO)5. Bimetallic catalytic binuclear elimination as an origin for synergism in homogeneous catalysis. Journal of the American Chemical Society 125 (18) : 5540-5548. ScholarBank@NUS Repository. https://doi.org/10.1021/ja029499i
Abstract: The bimetallic origins of catalytic synergism were studied using unmodified rhodium and manganese carbonyls as catalyst precursors during the low-temperature hydroformylation of 3,3-dimethylbut-1-ene to 4,4-dimethylpentanal in n-hexane solvent (T ≈ 298 K, Pco = 1.0-4.0 MPa, PH2 = 0.5-2.0 MPa). A dramatic increase in the catalytic rate was observed in the experiments conducted when both metals were used simultaneously. Detailed in-situ FTIR measurements indicated the observable presence of only homometallic complexes during catalysis, e.g., RCORh(CO)4, Rh4(CO)12, Rh6(CO)16, HMn(CO)5, and Mn2(CO)10. The kinetics of product formation show a distinct linear-bilinear form in observables: k1[RCORh(CO)4][CO]-1[H2] + k2[RCORh(CO)4][HMn(CO)5][CO]-1.5. The first term represents the classic unicyclic rhodium catalysis, while the second 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 and not cluster catalysis. This appears to be the first detailed evidence for such a catalytic mechanism, and its implications for selectivity and nonlinear catalytic activity are accordingly discussed.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/92428
ISSN: 00027863
DOI: 10.1021/ja029499i
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