Rhodium complex hydroformylation

P-31 NMR Studies of Equilibria and Ligand Exchange in Triphenylphosphine Rhodium Complex and Related Chelated Bisphosphine Rhodium Complex Hydroformylation Catalyst Systems... 

Triphenylphosphine -rhodium complex hydroformylation catalyst systems discovered by Wilkinson and developed by Union Carbide, Davy Powergas, and Johnson Matthey... 

P NMR Studies of Catalytic Intermediates in Triphenylphosphine Rhodium Complex Hydroformylation Systems... 

Advances in Chemistry, Editors Alyea, E. C., and Meek, D. W., American Chemical Society, 1981, 196, 78, paper of "31p NMR Studies of Equilibria and Ligand Exchange in Triphenyl phosphine Rhodium Complex and Related Chelated Bis-Phosphine Rhodium Complex Hydroformylation Catalyst Systems," by Kastrup, R. V., Merola, J. S., and Oswald, A. A., in press. 

Rhodium complex Hydroformylation Olefin + products Sodium n-dodecyl 79... 

Rhodium complex Hydroformylation Olefin+ Sodium n-dodecyl sulfate 7-120 > 79... 

An early attempt to hydroformylate butenediol using a cobalt carbonyl catalyst gave tetrahydro-2-furanmethanol (95), presumably by aHybc rearrangement to 3-butene-l,2-diol before hydroformylation. Later, hydroformylation of butenediol diacetate with a rhodium complex as catalyst gave the acetate of 3-formyl-3-buten-l-ol (96). Hydrogenation in such a system gave 2-methyl-1,4-butanediol (97). 

A new homogeneous process for hydroformylation of olefins using a water-soluble catalyst has been developed (40). The catalyst is based on a rhodium complex and utilizes a water-soluble phosphine such as tri(M-sulfophenyl)phosphine. The use of an aqueous phase simplifies the separation of the catalyst and products (see Oxo process). 

Polymer-supported catalysts incorporating organometaUic complexes also behave in much the same way as their soluble analogues (28). Extensive research has been done in attempts to develop supported rhodium complex catalysts for olefin hydroformylation and methanol carbonylation, but the effort has not been commercially successful. The difficulty is that the polymer-supported catalysts are not sufftciendy stable the valuable metal is continuously leached into the product stream (28). Consequendy, the soHd catalysts fail to eliminate the problems of corrosion and catalyst recovery and recycle that are characteristic of solution catalysis. 

There are currentiy no commercial producers of C-19 dicarboxyhc acids. During the 1970s BASF and Union Camp Corporation offered developmental products, but they were never commercialized (78). The Northern Regional Research Laboratory (NRRL) carried out extensive studies on preparing C-19 dicarboxyhc acids via hydroformylation using both cobalt catalyst and rhodium complexes as catalysts (78). In addition, the NRRL developed a simplified method to prepare 9-(10)-carboxystearic acid in high yields using a palladium catalyst (79). 

C-19 dicarboxyhc acid can be made from oleic acid or derivatives and carbon monoxide by hydroformylation, hydrocarboxylation, or carbonylation. In hydroformylation, ie, the Oxo reaction or Roelen reaction, the catalyst is usually cobalt carbonyl or a rhodium complex (see Oxo process). When using a cobalt catalyst a mixture of isomeric C-19 compounds results due to isomerization of the double bond prior to carbon monoxide addition (80). 

Hydroformylation, or the 0X0 process, is the reaction of olefins with CO and H9 to make aldehydes, which may subsequently be converted to higher alcohols. The catalyst base is cobalt naph-thenate, which transforms to cobalt hydrocarbonyl in place. A rhodium complex that is more stable and mnctions at a lower temperature is also used. 

J. Herwig, R. Eischer in Rhodium-catalyzed Hydroformylation in Catalysis by Metal Complexes (P. W. N. M. van Leewen, C. Claver eds.), Kluwer Academic Publisher, The Netherlands,... 

A simplified mechanism for the hydroformylation reaction using the rhodium complex starts by the addition of the olefin to the catalyst (A) to form complex (B). The latter rearranges, probably through a four-centered intermediate, to the alkyl complex (C). A carbon monoxide insertion gives the square-planar complex (D). Successive H2 and CO addition produces the original catalyst and the product ... 

Phosphine, amino-rhodium complexes catalysts, hydroformylation, 6,261 Phosphine, 3-aminopropyldimethyl-photographic fixer, 6,100 Phosphine, bis(2-carboxyethyl)methyl-photography... 

Styrene, a-ethyl-asymmetric hydroformylation catalysts, platinum complexes, 6, 266 asymmetric hydrogenation catalysts, rhodium complexes, 6, 250 Styrene, a-methyl-asymmetric carbonylation catalysis by palladium complexes, 6, 293 carbonylation... 

In the hydroformylation of lower alkenes using a modified cobalt catalyst complex separation is achieved by distillation. The ligands are high-boiling so that they remain with the heavy ends when these are removed from the alcohol product. Distillation is not possible when higher alcohols or aldehydes are produced, because of decomposition of the catalyst ligands at the higher temperatures required. Rhodium complexes can usually also be removed by distillation, since these complexes are relatively stable. 

Scheme 10.2 Rh-catalysed hydroformylation of styrene with dithiolate rhodium complexes.

Rhodium complexes of (R,i )-1-benzyl-3,4-dithioether-pyrrolidines were also prepared by these authors, who further investigated them as ligands of rhodium complexes in the hydroformylation of styrene but, in all experiments, the enantioselectivity was lower than 3% ee, whereas the chemoselectivity was of 97% (Scheme 10.5). ... 

It was also evaluated how phosphorylation of the arylphosphole ligands (17b,d) affects the activity of the in situ rhodium complex in the hydroformylation of styrene (Scheme 20). 

The new family of phospholes with 2,4,6-trialkylphenyl substituent on the phosphorus atom show, in many respects, a special reactivity. Due to the flattening of the P-pyramid, the arylphospholes exhibit aromaticity and hence underwent Friedel-Crafts reactions. The regioselective functionalization through reaction with phosphorus tribromide gave a variety of phospholes with an exocyclic P-moiety. Novel phosphole platinum and rhodium complexes were prepared and a part of them was tested in hydroformylation reactions. 

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