Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/92417
Title: The competitive and non-competitive hydroformylation of conjugated dienes starting with tetrarhodium dodecacarbonyl. An in-situ high-pressure infrared spectroscopic study
Authors: Liu, G.
Garland, M. 
Keywords: Deactivation
Dienes
Hydroformylation
Rhodium complexes
Tetrarhodium dodecacarbonyl
Issue Date: 25-Aug-2000
Source: Liu, G.,Garland, M. (2000-08-25). The competitive and non-competitive hydroformylation of conjugated dienes starting with tetrarhodium dodecacarbonyl. An in-situ high-pressure infrared spectroscopic study. Journal of Organometallic Chemistry 608 (1-2) : 76-85. ScholarBank@NUS Repository.
Abstract: It is well known that the liquid-phase homogeneous unmodified rhodium catalysed hydroformylation of alkenes is poisoned by the presence of trace quantities of conjugated dienes. Nevertheless, some hydroformylation of conjugated dienes is possible with unmodified rhodium, and this reaction is in general slower than alkene hydroformylations at comparable reaction conditions. In the present contribution, we examined (A) the catalytic behaviour of alkenes in the presence of trace conjugated diene impurities and (B) the catalytic behaviour of a variety of dienes using Rh4(CO)12 in n-hexane solvent at 293 K under 1.0-4.0 MPa CO and 0.5-2.0 MPa H2. The analytic method was in-situ high-pressure infrared spectroscopy. It was observed that (I) in the hydroformylation of poisoned alkenes, most of the rhodium reacts with the trace quantity of conjugated dienes and not the alkenes in this competitive situation and (II) the metal carbonyl spectra of the hydroformylation of a variety of dienes are very similar. The primary absorbance maxima observed in the hydroformylations of conjugated dienes occur at circa 2109, 2091, 2087, 2064, 2049, 2037, 2030, 2020, 2012, 1999, and 1990 cm-1. Given the known chemistry Of Rh4(CO)12 under syngas, and the very well documented chemistry of Rh4(CO)12 under alkene hydroformylation conditions, the lack of bridging carbonyls in the present experiments strongly suggested that the new infrared vibrations are due to mononuclear rhodium species. Preliminary analysis suggests the presence of at least three new species. In particular, the formation of observable η3 allyl rhodium tricarbonyl species, σ allyl rhodium tetracarbonyl species and even acyl rhodium tetracarbonyl species RCORh(CO)4 (R = alkenyl and/or formylalkyl) seems probable. Characteristic wavenumbers of 2108, 2064, 2037, 2020 and 1700 cm-1 are tentatively assigned to the latter. The reduced hydroformylation activity in the competitive hydroformylation of alkenes arises due to the much higher affinity of rhodium complexes for conjugated dienes than for alkenes under otherwise similar reaction conditions. © 2000 Elsevier Science S.A. All rights reserved.
Source Title: Journal of Organometallic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/92417
ISSN: 0022328X
Appears in Collections:Staff Publications

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