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United States Patent (19) 11 Patent Number: 4,889,957 Besson Et Al

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United States Patent (19) 11 Patent Number: 4,889,957 Besson Et Al United States Patent (19) 11 Patent Number: 4,889,957 Besson et al. (45) Date of Patent: Dec. 26, 1989 54 DINUCLEAR AND WATER-SOLUBLE 56 References Cited RHOOUM COMPLEXES AND U.S. PATENT DOCUMENTS HYDROFORMYLATION CATALYSS THEREWTH 4,778,905 10/1988 Besson et al. ......................... 556/16 Primary Examiner-Werren B. Lone (75) Inventors: Bernard Besson, Villeurbanne; Attorney, Agent, or Firm-Burns, Doane, Swecker & Philippe Kalck, Auzeville; Alain Mathis Thorez, Montgiscard, all of France 57 ABSTRACT 73) Assignee: Rhone-Poulenc Chimie de Base, Novel dinuclear and water-soluble rhodium complexes, Courbevoie, France well suited as hydroformylation catalysts, as are aque ous solutions thereof, have the general formula: 21 Appl. No.: 213,149 22 Filed: Jun. 29, 1988 (D TAPS-1NR,TAPS Related U.S. Application Data L1 s NL 62) Division of Ser. No. 788,202, Oct. 16, 1985, Pat. No. R 4,778,905. in which R and R', which are identical or different, are each a substituted or unsubstituted hydrocarbon radical, (30) Foreign Application Priority Data with the proviso that R and R may together form a Oct. 16, 1984 FR France ................................ 84 16007 single divalent radical, TAPS is a sulfonated triaryl phosphine ligand, and L is a carbonyl (CO) or a TAPS (51 Int. Cl* .................... CO7C 45/50 ligand. 52 U.S. C. ....................................... 568/454; 556/16 58 Field of Search ........................... 568/454; 556/16 3 Claims, No Drawings 4,889,957 1. DNUCLEAR AND WATERSOLUBLE RHODUM COMPLEXES AND HYDROFORMYLATON CH2Cl CATALYSS THEREWITH This application is a division of application Ser. No. 788,202 filed Oct. 16, 1985, U.S. Pat. No. 4,778,905. BACKGROUND OF THE INVENTION O and their use as hydroformylation catalysts are de 1. Field of the Invention: scribed in U.S. Pat. No. 4,215,066. However, while the fundamental interest in these The present invention relates to dinuclear and water rhodium complexes is not in doubt, the development of soluble rhodium complexes, and to the use of such com 15 their use as catalysts on an industrial scale is hindered by plexes or aqueous solutions thereofas hydroformylation their lack of selectivity. In fact, the ration/n --iso (n: catalysts. normal linear aldehyde; iso: branched aldehyde) which complexes of this type provide in hydroformylation 2. Description of the Prior Art: reactions is notoriously inadequate, which severely Dinuclear rhodium complexes of the type (1): 20 burdens the overall economics of this process. Furthermore, the recovery and the recycling of the complexes of the type (2) are complicated by difficulties Cl2Sn C N / N SnCl2 (1) traditionally associated with homogeneous catalysis Rh reactions, difficulties whose severity is further increased / N / YN 25 by the fact that the loss of even the smallest quantity of Cl2Sn Cl SnCl2 rhodium is economically prohibitive. It might have been thought possible to remedy these and their use as a hydroformylation catalyst are de disadvantages, at least insofar as the catalyst recovery scribed in U. S. Pat. No. 3,501,581. However, these and recycling are concerned, by using complexes of the catalysts have low activity. 30 type (3) above, namely, compounds in which the or ganometallic complexes are "immobilized' on a solid Dinuclear rhodium complexes of the type (2): organic (or mineral) support through the intermediacy of functional groups in the said support. It is generally t (2) observed, however, that a significant part of the metal 35 goes into solution in the liquid reaction phase (see, par P(OCH3)3 S P(OCH3)3 N / N / ticularly W. H. Lang etal, J. Organomet. Chem., 134, 85 R. R. (1977)). / N / N In addition, as taught by J. Fallbe in New Synthesis P(OCH3)3 P(OCH3)3 with Carbon Monoxide, Springer Verlag (1980), the cata t-Bu lyst solids thus obtained are much more sensitive to deactivation and poisoning than similar soluble cata (in which t-Bu denotes a tert-butyl radical) or of the lysts. It will be seen, therefore, that the merit of such "sup type (3): ported complexes' cannot be established industrially, 45 all the more so since their use involves difficulties in P(OCH3)3 N POCH) connection with mass and/or heat transfers. Rh SUMMARY OF THE INVENTION / N CH-S S-CH2 Accordingly, a major object of the present invention N / Rh 50 is the provision of novel dinuclear and water-soluble / N rhodium catalyst complexes; the use of such complexes P(OCH3)3 P(OCH3)3 and/or aqueous solutions thereof to catalyze the hy droformylation of olefins avoids those disadvantages and drawbacks to date characterizing the state of this 55 art. in which: (3) The novel rhodium complexes according to this in vention not only make it possible to attain high n/n - iso ratios upon use thereof as hydroformylation cata lysts, with an activity which is slightly superior to that CH 60 obtained (all conditions being otherwise equal) when using a mononuclear complex, but also permit easy separation of the various end-products of the reaction. CS Indeed, the facts that the reactants and the reaction products are present in an organic liquid phase and/or 65 in a gaseous phase, and that the catalyst system can be found wholly (or virtually wholly) in an aqueous liquid denotes a residue derived from chloromethylated poly phase, enable the separation thereof simply by stopping styrene: the stirring of the reaction mixture and, where applica 4,889,957 3 4. ble, by releasing the pressure; the use of completely The preferred TAPS ligands correspond to the for liquid phases promotes mass and heat transfers. mula (II) above, in which: Briefly, the present invention features dinuclear and (i) Arl, Ar2 and Ars are phenyl groups; water-soluble rhodium complexes having the general (ii) Y1, Y2 and Y, which are identical or different, are formula (I): each alkyl radicals containing from 1 to 2 carbon atoms, alkoxy radicals containing from 1 to 2 carbon atoms or chlorine atoms; (I) (iii) M is a cation selected from among the hydrogen TAPS-1SriTAPS cation, the ammonium cation, the cations derived from L1 NL 10 sodium, potassium, calcium and barium, and the quater nary ammonium cations of formula NOR3R4R5R6) in R which R3, R4, R5 and R6, which are identical or differ ent, are each straight or branched chain alkyl radicals in which R and R', which are identical or different, are containing at most 4 carbon atoms; and each a hydrocarbon or a substituted such hydrocarbon 15 (iv) m1, m2 and m3 are integers ranging from 0 to 3, radical bearing one or more substituents which do not inclusive. interfere with the intended uses of the complexes in The TAPS ligands which are most particularly pre question, with the proviso that R and R may together ferred correspond to the formula (II) above, in which: form a single divalent radical; TAPS is a sulfonated Ari, Ar2 and Ars are phenyl groups; triarylphosphine ligand; and L is a carbonyl (CO) ligand 20 m1, m2 and m3 are Zero; or a TAPS ligand. This invention also features the use M is selected from among the cations derived from of these complexes or of the aqueous solutions thereof sodium, potassium, calcium, barium, the ammonium to catalyze the hydroformylation of unsaturated com cation and the tetramethyl and tetraethyl ammonium pounds. cations; and 25 the SO3 group(s) is (are) in the meta position. DETAILED DESCRIPTION OF THE As other examples of suitable TAPS ligands, repre INVENTION sentative are the alkali metal or alkaline earth metal More particularly according to the present invention, salts, ammonium salts, and the quaternary ammonium the sulfonated triarylphosphine ligands which are par salts of the following sulfonated phosphines: ticularly suitable are represented by the formula (II): 30 (m-sulfophenyl)diphenylphosphine, (p-sulfophenyl)diphenylphosphine, (m-sulfo-p-methylphenyl)di(p-methylphenyl)phos (SO3M)n1 (II) phine, Ar1 N (m-sulfo-p-methoxyphenyl)di(p-methoxyphenyl)phos 35 phine, (Yi)in (m-sulfo-p-chlorophenyl)di(p-chlorophenyl)phosphine, di(m-sulfophenyl)phenylphosphine, di(p-sulfophenyl)phenylphosphine, di(m-sulfo-p-methylphenyl)(p-methylphenyl)phos phine, di(m-sulfo-p-methoxyphenyl)(p-methoxyphenyl)phos phine, di(m-sulfo-p-chlorophenyl)(p-chlorophenyl)phosphine, tri(m-sulfophenyl)phosphine, 45 tri(p-sulfophenyl)phosphine, tri(m-sulfo-p-methylphenyl)phosphine, in which Arl, Ar2 and Ars, which are identical or differ tri(m-sulfo-p-methoxyphenyl)phosphine, ent, are each carbocyclic aryl groups; Y1, Y2 and Y3, tri(m-sulfo-p-chlorophenyl)phosphine, which are identical or different, are each a straight or (o-sulfo-p-methylphenyl)(m-sulfo-p-methylphenyl branched chain alkyl radical containing from 1 to 4 50 (m,m'-disulfo-p-methylphenyl)phosphine, carbon atoms, an alkoxy radical containing from 1 to 4 (m-sulfophenyl)(m-sulfo-p-chlorophenyl)(m,m'-di-sul carbon atoms, a halogen atom a hydroxyl group, a ni fo-p-chlorophenyl)phosphine. trile group, a nitro group or a disubstituted amino group Of course, mixtures of these phosphines may also be of the formula -NRR2 wherein R1 and R2, which are used In particular, a mixture of (m-sulfophenyl)di identical or different, are each a straight or branched 55 phenylphosphine, di(m-sulfophenyl)phenylphosphine chain alkyl radical containing at most 4 carbon atoms; and tri(m-sulfophenyl)phosphine may be employed. M is a cationic residue of inorganic or organic origin, The dinuclear and water-soluble rhodium complexes selected from among hydrogen and the inorganic cati according to the present invention incorporate two ons derived from alkali metals or alkaline earth metals, mu-thiolato bridges denoted by -SR and -SR' in the or derived from lead, zinc or copper, the ammonium general formula (I), R and R' being as above-defined.
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