PROCESS FOR THE PRODUCTION OF ALDEHYDES BY HYDROFORMYLATION IN PRESENCE OF RHODIUM COMPOUND

Abstract: This invention relates to rhodium compounds having the general formula: HRh(CO)(XR₃) n (YR′₃) 3-n wherein X is phosphorus, arsenic or antimony; Y is arsenic or antimony when X is phosphorus, Y is phosphorus or anti­ mony when X is arsenic, or Y is phosphorus, arsenic or anti­ mony when X is antimony; R and R′ are aryl groups; and n is an integer of 1 or 2. Further, it relates to the hydroformylation of olefins in the presence of a rhodium catalyst, such as HRh(CO)(PPh₃)₂(AsPh₃) / excess PPh₃ and AsPh₃ or HRh (CO)(PPh₃)(AsPh₃)₂ / excess PPh₃ and AsPh₃. An oxo process may be carried out in the presence of a rhodium source and said free mixed ligands. For example, HRh(CO)PPh₃)₃ with excess AsPh₃/PPh₃ may be used.

Description: This invention relates to new rhodium compounds and a process ror producing the same. More particularly, it is concerned with new rhodium compounds having a structure iso electronic to ERh(CO)(PPh3)3 and a process ror the selective production of the same. Further, it relates to use of such products as catalysts in the oxo process. Carzonyl tris (triphenylphosphine) rhodium hydride is knawn as a catalyst having activity in various chemical reactions Xor organic syntheses, for example, in hydroformyla- tion. (Japanese Patent Publication No. 10730/1970 equivalent to U.S. Patent 3,527,809). See also U.S. Patent 3,821,3L1 and Canadian Patent 992, 101. As rhodium compounds having a structure isoelectronic thereto are known carbonyl tris(triphenyl- phosphite) rhodium hydride HRh(CO)(P(OPh)3)3 (britisch Patent No. 1338225), carnonyl tris (triphenylarsine) rhodium hydride HRh(CO)(AsPh3)3 and carbonyl tris (triphenylarsite) rhodium hydride HRh(CO) (As(OPh)3)3 (British Patent No. 1357735). As to producing these compounds, same processes are known. In the case of Eth(CO)(PPh3)3, for example, there have been proposed (1) a process comprising reacting rhodium trichloride. t-;nydrate, excess triphenylphosphine, an aqueous solution of formaldehyde and sodium borohydride in boiling ethanol (Journal of the Chemical Society (A), 1968, page 2660), (2) a process comprising reacting carbonyl bis (triphenylphosphite) rhodium# chloride, excess t-iphenyphosphine and sodium borohydride in boiling ethanol (ibid) and (3) a process comprising contacting carbonyl bis(triphenylphosphite) rhodium chloride and excess triphenylphosphine with synthesis gas (mixture of H2 and CO) at a temnerature of at least 5OçC under a pressure of at least 10 atm. (Jypanese Patent Publication No. 17572/1978). However, carbonyl tris(triphenylstibine) rhodium hydride HRh(CO(SbPH3)3 having a structure isoelctronic to the above described rhodium compounds has not beçn synthesized and isolated. Moreover, as ns evident from the foregoing description, alt the rhodium compounds having the above described known structures contain respeotively a single kind of ligand and those containing different kinds of mixed ligands, for example, phosphines and arsines in the same mole- cule, are not known, although some monovalent rhodium compounds containing mixed ligands in the same molecule are known, for example, carbonyl triphenylphosphine triphenyl sine rhodium chloride RhCl(CO)(PPh3) (AsPh3) (Journal of Organometallic Chemistry, Vol. 43, No. 2, 197Z, page 425), carbonyl triphenylphosphine triphenylstibine rhodium chloride RhCl(CO)(PPh3) (SbPh3) (ibid), carbonyl triphenylarsine tri phenylstibine rhodium chloride RhCl(CO)(AsPh3)(SbPh3) (ibid) and carbonyl (diethylphenylphosphine) (tri-o-toluylstibine) rhodium chloride RhCl(CO)(PPhET2) (Sb(o-CH2C6H4)3) (Inorganic Chemistry, Vol. 15, No. 13, 1976, page 646,. See also J. Chem. Soc. D1970, (17), 1077-8 (England); Inorg. Nucl. Chem. Lett. 1971, 7(9)877-9 (England); J. Chew. Soc. Dalton Trans. 1972 (19) 2161-9 (England) and U.S. Patent 3,459,780. As a method for synthesizing these compounds, it has been proposed to add to a binuclear rhodium compound (R+SCl(CO)L)2 wherein L is triphenylphosphine, triphenylsrsine or triphenylstibine in warn benzene an ether solution of 2 mols (equimolar amount) of L' being triphenylphosphine, triphenylsrsine or triphenylstibine but not the s me as L (Journal of Organometallic Chemestry, Vol. 43, No. 2, 1972, page 425). Other references of lesser interest, noted because they concern rhodium-containing compounds, are U.S. Patents 3,939,188 and 3,946,082, which relate to compounds containing reduced, zero valent rhodium and 4,052,461 which relates to ionic rhodium compounds but not the hydrides which are nonionic. However, mined ligands-containing rhodium compounds having a structure isoelectronic to HRh(CO)(PPh3)3 or three stibines-coordinated rhodium compounds cannot be obtained, or mixtures of various rhodium compounds are only obtained, by the above described method or other known methods and it is very difficult to isolate such compounds in a pure form. Rhodium-phosphine type or rhodium-phosphite type complexes are known as catalysts ror the hydroformylation of olefins. The stability of a rhodium catalyst is increased by modification with phosphine, arsine, or stlbine, which permits practicing the oxo reaction at a rather low pressure. According tO Japanese Patent No. 903,32Z, straight chain-rich aldehydes are prepared at a low total pressure with a low partial pressure of carbon monoxide and a high partial pressure of hydrogen in the presence of a rhodium triarylphosphine catalyst and a triarylphosphine ligand in a large excess to the rhodium. However, this method has the disaÅavantage that the hydroformylation reaction rate of an olefin is markedly decreased because of using a ligand in a large excess to rhodi.qn, and a considerable quantity of a paraffin is formed by the hydrogenation of the olefin ("Rydrocarhon Processing" (4) 112 (1970 due to the reaction at a law total pressure with a low partial pressure of carbon monoxide and a high partial pressure of hydrogen. Rhodium catalysts in combination with arsines or stibines instead of phosphines have been proposed, but the studies thereof have not been made so intensively because of their lower activity compared with tertiary phosphine-rhodium catalysts. Applicants have made various efforts to obtain new rhodium compounds having a structure isoelectronic to ERhiCO) i (PPh3)3 and, as a result, hlve succeeded in obtaining new rhodium compounds representes by the following general formula in high yield and in a pure form, thus accomplishing the present i invention. It is estimated that in the new compounds the rhodium is mono-vatent. This invention further relates to a process for the production of aldehydes by the hydroforaylation of olefins and more particularly, it is concerned with an improved process for producing aldehydes by reacting olefins, carbon monoxide and hydrogen in the presence of rhodium containing complex compound catalysts and rree ligands. That is to say, the gist of the present invention consists in novel rhodium compounds represented by the general formula, HRh(CO)(XR3)n(YR'3)3-n (A) wherein X is phosphorus, arsenic or antimony; Y is arsenic or antimony when X is phosphorus, Y is phosphorus or antimony when X is arsenic or Y is phosphorus, arsenic or antimony when x is antimony; R and R' are aryl groups, which m2y be the same or different; and n is an integer of 1 or 2, and a process for their production. Further, applicants have made studies of hydroformyla- tion using a catalyst system comprising rhodium and mixed ligands of tertiary organo phosphorus ligands and tertiary organo arsenic ligands in combination and have found that, surprisingly, when hydroformylation of an olefin is carried out with this catalyst system in the presence of excess mixed ligands, the reaction rate is remarkably improved, the quantity or paraffin formed by the hydrogenation -of the olefin is decreased and, in addition, the selectivity to normal chain aldehyde is kept similar or improved in comparison with carrying out the reaction nn the presence of a tertiary organo phosphorus rhodium catalyst and excess tertiary organo phosphorus ligand. Also, the catalyst can be re-used with maintenance of its activity after separating the prepared aldehyde by suitable means such as distillation and the like. Therefore, the present invention provides a commer cially valuabLe process whereby hydroformylation of an olefin i8 improved using a rhodium complex containing both a tertiary organo phosphorus compound and tertiary organo arsenic compound in a rhodium complex HRh(CO)(ligand)3 which is an active species for the hydroformylation in the presence of an excess quantity of mixed ligands of a tertiary organo phosphorus com pound and tertiary organo arsenic compound. That is to say, the present invention relates to a process for producing aldehydes by reacting an olefin with carbon monoxide and hydrogen, the aldehydes having one more carbon atom than the olefin, which comprises carrying out the reaction using a rhodium catalyst containing a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula X'R'13 (wherein X' represents phosphorus or arsenin and R" represenrs an organic group, in particular, alkyl, cycloalkyl, aryl or aralkyl group, which may be same or different) and carbon monoxide in the presence or free mixed ligands comprising a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula X'R"3 3 (wherein R" has the same meaning as just described anÅa may be snme as or different from those contained in the above described rhodium catalyst) in excess of the quantity required for coordination to the rhodium atom. Figs. 1 and 2 are graphs showing the relationships between the sum of the Pawling electro-negativities and #C=O and #Rh-H respectively of compounds of this invention. The novel rhodium compounds included in the above described general formula (A) are class fief o the rollow- ing seven groups: (I) HRh(CO)(PR3)2(AsR 3/ (II) HRh(CO)(PR3)(AsR'3)2 (III) HRh(CO)(PR3)2(SbR'3)2 (IV) HRh(CO)(PR3)(SbR'3)2 2 (V) HRh(CO)(AsR3)2(SbR'3) (VI) HRh(CO)(AsR3)(SbR'3)2 (VII) HRh(CO)(SbR3)3 (R and R' have the same meanings as described above.) Useful examples of these compounds, in particular where R and R' are the same and are phenyl groups, are as follows: : (1) Carbonyl bis(triphenylphosphine) triphenylarsine rhodium hydride HRh(CO)(PPh3)2(AsPh3) (2) Carbonyl bis(triphenylphosphine) triphenYlstibine rhodium hydride HRh(CO)(SbPh3)(PPh3)2 (3) Carbonyl bis(triphenylarsine) triphenylphosphine rhodium hydride HRh(CO)(PPh3)(AsPh3)2 (4) Carbonyl bis(triphenylarsine) triphenylstibine rhodium hydride HRh(CO)(SbPh3)(AsPh3)2 (5) Carbonyl bis(triphenylstibine) triphenylphosphine rhodium hydride HRh(CO)(PPh3)(SbPh3)2 (6) Carbonyl bis(triphenylstibine) triphenylarsine rhodium hydride HRh(CO)(AsPh3)(SbPh3)2 (7) Carbonyl tris(triphenylstibine) rhodium hydride HRh(CO) SbPh3)3 The structural formulas of these Seven kinds of the novel compounds were confirmed by an IR spectsophotmmeter and elementary analysis, results shown in Table5 1 znd 2 being obtained. As can be seen from Table 1, the IR data of the compounds of the present invention show that the absorption based on the streching frequency of Rh-H (# Rh-H) appears near 2000 cm-1, the absorption based on the streching frequency of C=O (# C=O) appears near 1900 cm-1 and the absorption zones are substantially similar to those of #Rh-H and #C=O of the known compounds HRh(CO)(PPH3)3 and HRh(CO)(AsPh3)3. In addition, there is a linear relationship between the sum of the Pauling electro-negativities of the elements and # C=O or #Rh-H in these compounds, respectively as shown on Fig. 1 and Fig. 2 (In Fig. 1 and Fig. 2, P3 = HRh(CO)(PPH3)3*, P2As " HRh(CO)(PPh3)2(AsPh3), As2P = HRh(CO)(AsPH3)2(PPh3), P2Sb = HRh(CO)(PPh3)2(SbPh3), As3 = HRh(CO)(AsPH3)3*, SbP = HRh(CO) (SbPh3)2 - (PPh3), As2Sb = HRh(CO)(AsPh3)2(SbPH3), Sb2As = HRh(CO)(SbPh3)2(AsPh3), Sb3 = HRh(CO) (SbPh3)3, mark * = known compound). As apparent from Table 2, the found values in the elementary analysis of these compounds coincide exactly with calculated ones and thus it is confirmed that the compounds o the present invention have the designated general formula. For the production of these compounds, the various known methods or the method comprising reacting a monovalent rhodium compound containing mixed ligands and excess ligands in the presence of sodium borohydride or hydra2ine in boiling ethanol has the disadvantage set forth above that starting materials only are recovered, starting materials themselves e decomposed, or a mixture of various rhodium compounds is only obtained and isolation of the desired compound is very difficult. However, applicants have found that these compounds can be obtained in high selectivity and high yield by first contacting a compound of the general formula RhZ(CO)(XR3)2 which Z is a halide anion selected from chloride, bromide and iodide, and X and R have the meanings given with a compound od the general formula YR'3 in which Y and R' have the meanings given in a selected amount depending on the above compound, ir a solvent, then adding a reducing agent carefully at a rela- tively low temperature and thereby reacting them. The molar ratio of YR'3 to RhZ(CO)(XR3)2 used in the present invention, depends on the properties of the starting materials and the rhodium compound to be formed. In order to obtain the desired compound in a pure form, it is desirable tc use YR'3 in at least the equimolar amount. When using YR'3 3 in too large an excess, however, the desired compound is obtained in a mixed state with the ligand, as a result of which a number of washings with a solvent will be needed. This is disadvantageous economically and, accordingly, the molar ratio is preferably 1.0 to 10. Addition of reducing agents before the contacting of RhZ(CO)(XR3)2 with YR'3 is not desirable because various reactions are thereby caused to take place resulting in deterioration of the reactants. Therefore it is very important to contact the two, suitably by the use of solvents, before adding a reducing agent. In the present invention, any solvents may be used which are capable of dissolving, at least partly, RhZ(COl(XR3)2 and/or YR'3 but do not react with them. Illustrative of such solvents are aromatic hydrocarbons such as benzene, toluene and lower alcohols such as methanol, ethanol, propanol, isopropanol. Preferred solvents are lower alcohols, and above all, ethanol may be used in view of advantages in practical opera- tion. The temperature of contact of RhZ(CO)(XR3)2 and YR'3 can be varied widely within the range in which they are not decomposed, but preferably ranges fram room temperature to about lOOeC, most preferably from-about 40 to about 80 C. Most useful examples of the reducing agent used in the present-invention are alkali metal borohydrides such as sodium borohydride, NaBH4, potassium borohydride, KBH4, and lithium borohydride; boranes such as borane, BH3, diborane, B2H6, and tetraborane, B4H10; and hydrides of Group IIIA elements such as aluminium, for example, lithium aluminium hydride. Sodium borohydride is preferred because of its cheapness and ease of handling. When the reducing agent is added at a high temperature after both the reactants are contacted, the heat of reaction sometimes brings about unfavorable side reactions and, therefore, it is desirable to cool to a temperature lower than room temperature, preferably around 0 C, prior to addition of the reducing agent. The quantity of reducing agent used in the present invention is not particularly limited since no side reaction occurs even if a large quantity of the reducing agent is added, but, in general, a proportion of 5 to 50 mols to 1 mol of RhZ(CO)(XR3)z is sufficient. The reducing agent can be added as a solid to the foregoing mixed solution, but is preferably added in the form of a solution in a lower alcohol, etc. In order to prevent the rapid generation of heat due to the reducing reaction, it is desirable to add the reducing agent gradually while controlling the temperature and stirring the solution adequately. After the reducing agent has been added, cooling may be stopped and the mixture allowed to return to room temperature. The stirring is preferably continued even after the reducing agent is added. This period of time is not particularly limited but usually 1 to 3 hours is sufficient. When these procedures are carried out, the desired rhodium compound is precipitated from the solution. The product obtained as a precipitate is separated by filtration and washed several times with a solvent to increase its purity. In the production of HRh(CO)(Sb23)3 it is desirable /3 to use a starting material in which z is a bromide or iodide anion. However, even if Z is a chloride anion, Z can readily be converted into a bromide or iodide anion by reaction with potassium bromide or potassium iodide. Thus, the above described seven groups of new rhodium compounds can be obtained in high yield. The rhodium catalyst used in the present invention may be prepared by synthesizing a rhodium complex represented by the general formula set forth below and combining this com- plex with excess mixed ligands. For example, the rhodium complex represented by the general formula: : HRh(CO)(PR1RêR )n(AsR4R5R6)3-n in which Rl, R2, R3, R4, R5 and R6 represent alkyl, cycloalkyl, R, B aryl and aralkyl groups and may be same or different, and n is 31 1 or 2, is made by first contacting RhZ(CO)(PRlR2R3)2 (wherein Z represents a halide anion) with AsR4R5R6 in a solvent, fol- lowed by gradually adding a reducing agent of a hydride type of Group IIIA elements of the Periodic Table such as sodium;boro- hydride at a relatively low temperature. Preferably, R1, Rê, R , R4, R5 and R6 are aryl groups and more preferably the same 8 aryl group. In view of the rcactivìty and commercial avail ;ar gab y, it is most preferable that they are all phenyl groups, thus a combination of triphenylarsine and triphenylphosphine. The mixed ligands used in excess may be the same as or different from those contained in the rhodium complex, but the same combinations are advantageous commercially. The ratio of tertiary organo phosphorus to tertiary organo arsenic used as mixed ligands in excess may be chosen within a wide range such that a rhodium complex containing mixed lngands is sub stantially present. This proportion is generally 20 : 1 to 1 : 20, preferably 10 : l to 1 : 10 snd a range of 2 : 1 to 1 : 2 is most preferable. The sum of the amounts of mixed ligands to be added in excess of those capable of combining with a rhodium ntom through coordination in a rhodium complex may be chosen within a wide range such that the mixed ligands-containing complex is substantially present. In general, the sum of the amounts of rree mixed.ligands is 3 mols or more per rhodium atom in the mixed ligands-conts¯ning rhodium complex. Since addition of free mixed Ligands in too largo an excess is disadvantageous with respect to the reaction and cost, the excess amount is preferably 5 to 1000 mols, most preferably 50 to 500 mols per rhodium atom. As an alternative to using a previously prepared rhodium complex, an oxo catalyst can be formed in situ, i.2. under hydrofo ylation conditions. That is to say, it is possible to use a method comprising contacting a rhodium metal such as rhodium black or supported rhodium, an inorganic rhodium compound such as rhodium oxide or rhodium nitrate, an organic acid salt such as rhodium acetate or rhodium octoate, or a rhodium complex such as rhodilm carbonyl, rhodium dic bonyl acetylacetone or rhodium carbonyl triphenyl phosphine acetylacvtone, in the presence of the above described mixed ligands with a mixed gas of carbon monoxide and hydrogen at elevated temperature before or during hydroformylation. When a hydro-fo =.ylation reaction of an olefin is carried out using a catalyst according to this invention, the reaction rate is increased to 1.5 to 2 times as much as when a single ligand of tertiary organo phosphorus is used and, accordingly, a reactor can be reduced in size with the same output. Eurthermore, it is possible to decrease the quantity of rhodium catalyst to olefin and the concentration of rhodium in a catalyst bed. The quantity of a rhodium catalyst used in a hydroformylation, depending on the procedure and the variety of olefin used as a starting material, may be chosen - considering these conditions within a wide range. In a catalyst recycling process wherein an olefin, synthesis gas and rhodium catalyst are fed to a reaction tower, the reaction mixture is withdrawn from the head of the tower, cooled and subjected to reduced pressure to separate a gaseous component, and the liquid product is passed through a distillation column to distill off the product and to give a still residue containing the rhodium catalyst which is then withdrawn from the bottom cf the column and recirculated to the reaction tower, for example, the quantity of the rhodium catalyst may be 10 ppm to 57. by weight, preferably 50 ppm to 17. by weight as rhodium metal based on olefin fed. In a liquid fixed bed process wherein an olefin and synthesis gas are fed to a catalyst layer charged previously to a reaction tower and only the reaction product in the form of a mixture of gases and vapors is withdrawn from the top of the tower, the concentration of rhodium in the catalyst layer is generally 10 ppm to 57. by weight, preferably 50 ppm to 17. by weight. The catalyst system of the present invention may be used batchwise in addition to the continuous procedures described above and is also applicable to liquid, vapor or mixed phase processes. The reaction conditions may be the same as those in the case of using the rhodium-tertiary organo phosphorus type catalysts. That is to say, the reaction tem- perature is ordinarily room temperature to about 150 C., preferably 50 to 1300C., most preferably 80 to 1200C. and the total pressure is ordinarily normal pressure to about 100 atmospheres, preferably normal pressure to 50 atmospheres, most preferably normal pressure to 30 atmospheres. In addition, the hydrogen to carbon monoxide molar ratio is 10/1 to 1/10, preferably 10/1 to lJl. A solvent is not always indispensable, but in order to maintain stable operation, it is desirable to use a solvent. The solvent may be chosen from a wide range among those having no detrimental influence on hydroformylation, for example, saturated hydrocarbons such as hexane, decane and dodecane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene and diisopropylbenzene; and oxygen-containing compounds such as alcohols, ketones, esters and preferably products and high boiling point by-products of hydroformylaton. The catalyst system of the present invention can be adapted to oC-olefins such as ethylene, propylene, butene-l, hexene-l and octene-l, olefins with internal double bonds such as butene-2 and octene-2, and vinyl compounds such as styrene, acrylonitrile, acrylic acid esters and allyl alcohols. The present catalyst system is most suitable for obtaining aldehydes rich in normal chain type isomers from Cc -olefins. The process for the production of and the identification of the compounds according to the present invention are illustrated in detail in the following examples without limit- ing the scope of this invention. Examples of the hydroformylation process of this invention are also given. Example 1 Svnthesis of Starting Materials (1) Commercially available reagents were used as to rhodium chloride trihydrate RhC13h3H20, triphenylphosphine PPh3, triphenylars ine AsPh3 triphenylstibine SbPh3, sodium borohydride NaBH4 and potassium iodide KI. (2) Di-u-chloro-tetracarbonyl dirhodium (RhCl(CO)2)2 was pre pared from RhC1303H20. and CO by the method disclosed in Inorganic Synthesis, 8, 211 (1966). (3) Carbonyl bis(triphenylphosphine) rhodium chloride RhCl(CO) (PPh3)2 was prepared from RhCl3#3H2O, PPh3 and aqueous solution of formaldehyde by the method disclosed in Inor ganic Synthesis, 11, 99 (1968). (4) Carbonyl bis(triphenylarsine) rhodium chloride RHC1(CO) AsPh3)2 and carboxyl bis(triphenylstibine) rhodium chlor ille RhCl(CO)(SbPh3)2 were prepared from [RHCl(CO)2]2 of (2) and AsPh3 or SbPh3 by the method disclosed in Journal of Chemical Society (A), 2287 (1966). (5) Carbonyl bis(triphenylstibine) rhodium iodide RhI(CO) (SBPh3)2: 2.0 g (2.29 tol) of RhCl(Co)(SbPh3)2 of (4) and 0.42 g (2.53 mmol) of KI were charged in a 200 ml Erlenmeyer flask, to which 150 ml of acetone as a solvent was then added, and the mixture was reacted with agitation at room temperature for 7 hours. Thereafter, the reaction produc t was filtered, and the product retained on the filter paper was washed three times with acetone and dried under reduced pressure to obtain L.7 g of the de sired, black-brown compound. Svnthesis of New Rhodium Compounds (A) HRh(CO)(AsPh3)(PPh3)2 0.5 g (0.724 mmol) of RhCl(CO)(PPh3)2 of the foregoing (3) and 0.443 g (1.447 =ol) of AsPh3 were charged to a 300 ml three-necked flask, to which 150 ml of ethanol as a solvent was then added, and the mixture was reacted with agitation at a temperature of 65 C in a nitrogen stream for 2 hours. Then the flask was immersed in an ice bath to keep the temperature at 0 C and the mixture was further stirred; to it a solution of 0.5 g (13.21 mmol) of NaBH4 in 50 ml of ethanol was gradually added dropwise over a period of about 30 minutes. Thereafter the flask was withdrawn from the ice bath and the mixture was stirred at room temperature for 2 hours and subjected to filtration in a nitrogen stream. The product retained on the filter paper was washed three times with ethanol and dried under reduced pressure to obtain 0.60 g (0.623 mmol) of a yellow powder (Yield: 86 mol %). (B) HRh(CO) (Sb?h3) (PPh3)2 The procedure of the above described (A) was repeated except using 0.511 g (1.447 mmol) of SbPh3 instead of AsPh3 of (A), thus obtaining 0.71 g (0.703 mmol) of a yellow powder (Yield: 97 mol 7.). (C) HRh(CO)(PPh3)(AsPh3)2 The procedure of the above described (A) was repeated except using 0.5 g (0.642 mmol) of RhCl(CO)(AsPh3)2 of the foregoing (4) in place of RhCl(CO)(PPh3)2 of (A) and 0.253 g (0.965 mmol) of PPh3 in place of AsPh3, thus obtaining 0.53 g (0.527 mol) of a yellow powder (Yield: 82 mol % ). (D) HRh(CO)(SbPh3)(AsPh3)2 The procedure of the above described (A) was repeated except using 0.5 g (0.642 mmol) of RhCl(CO)(AsFh3)2 of the foregoing (4) in place of RhCi(CO)(PPh3)2 of (A) and 0.34 g (0.963 mmol) of SbPh3 in place of AsPh3, thus ob taining 0.64 g (0.583 mmol) of a yellow-ochre powder (Yield: 91 mol 7.). (E) HRh(CO) (PPh3) (SbPh3)2 The procedure of the above described (A) was repeated except using 0.5 g (0.573 mmol) of RhCl(CO)(SbPh3)2 of the foregoing (4) in place of RhCl(CO)(PPh3)2 of (A) and 0.301 g (1.148 mmol) of PPh3 in place of AsPh3, thus ob taining 0.511 g (0.464 =ol) of a light brown powder (Yield: 81 mol %). (F) HRh(CO;) (AsPh3) (SbPh3)2 The procedure of the above described (A) was repeated except using 0.5 g (0.573 mmol) of RhCl(CO)(SbPh3)2 of the foregoing (4) in place of RhCl(CO)(PPh3)2 of (A) and 0.35 g (1.143 mmol) of AsPh3, thus obtaining 0.40 g (0.350 mmol) of a brown powder (Yield: 61 mol :). (G) HRh(CO)(SbPh3)3 The procedure of the above described (A) was repeated except using 0.5 g (0.519 mmol) of RhI(CO)(SbPh3)2 of the foregoing (5) in place of RhCl(CO)(PPh3)2 of (A) and 0.367 g (1.039 mmol) of SbPh3 in place of AsPh3, thus obtaining 0.29 g (0.243 mmol) of a black-brown powder (Yield: 47 mol %). The decomposition temperatures and IR data (infrared spectra) of the compounds obtained by the above described procedures (A) to (G) are shown in Table l, the results of elementary analysis are shown in Table 2 and the relationships between the stretching frequencies of Rh-H and C=O of IR (#Rh-H and #C=O) and the sum of the electronegativities of P, As and Sb in the compounds are shown in Fig. 1 and Fig. 2. As is apparent from these tables and figures, the compounds of the present invention are all single compounds. Table 1 Decomposition2 IR Data3,4(cm-1) Rhodium Temperature Compound Color ( C) #Rh-H #C=0 HRh(CO)(AsPH3) Yellow 116-118 2023(Sh), 1919(S) (PPh3)2 2000(S) HRh(CO)(SbPh3) Yellow 131-133 1994(S) 1913(S) (PPh3)2 HRh(CO)(PPh3) Yellow 113-115 2010(Sh), 1916(5) (AsPh3)2 1998(S) IRh(CO)(SbPh3) Yellow- 132-134 1988(S) 1897(W) (AsPh3)2 ochre HRh(CO)(PPh3) Light 126-128 1994(5) 1918(M) (SbPh3)2 brown HRh(CO)(AsPh3) Brown 143-145 1985(5) 1892(W) (SbPh3)2 HRh(CO) Black- 168-171 1982(S) 1884(W) (SbPh3)3 brown HRh(CO)(PPh3)3* Yellow 137-138 2040(5), 1923(5) 2005(S) HRh(CO)(AsPh3)3* Yellow 130-132 1992(S) 1903(S) Remarks: * = Known Compound 2) Decomposition Temperature corresponds to. the ordinary melting point since these compounds all melt with decomposition. 3) IR Data were measured in the form of a tablet with KBr and calibrated by CO. 4) Letters in parentheses in IR Data show the absorption intensity of peak: S = strong; M = medium; W = weak; Sh = shoulder. Table 2 Rhodium Compound Found (%) Calculated (%) C H P As Sb Rh C H P As Sb Rh HRh(CO) (AsPh3)(PPh3)2 68.61 4.92 6.29 7.88 - 10.84 68.62 4.82 6.43 7.78 - 10.69 HRh(CO) (SbPh3)(PPh3)2 65.20 4.58 6.17 - 12.22 10.25 65.43 4.59 6.14 - 12.06 10.19 HRh(CO) (PPH3)(AsPh3)2 65.73 4.76 3.31 14.72 - 10.33 65.62 4.61 3.08 14.88 - 10.22 HRh(CO) (SbPh3)(AsPh3)2 59.96 4.09 - 13.80 11.37 9.52 60.19 4.23 - 13.65 11.09 9.38 HRh(CO) (PPh3)(SbPh3)2 60.07 4.25 3.00 - 21.89 9.38 60.03 4.22 2.82 - 22.13 9.35 HRh(CO) (AsPh3)(SbPh3)2 57.52 3.94 - 6.30 21.53 9.08 57.73 4.05 - 6.55 21.28 8.99 HRh(CO) (SbPh3)3 55.19 3.74 - - 30.57 8.88 55.46 3.89 - - 30.67 8.64 Comoarative Example 1 Using starting materials, solvent and quantity of reducing agent similar to those of Example 1(B), a mixture of RhCl(CO)(PPh3)2 and SbPh3 in ethanol was held at the boiling temperature, to which an ethanol solution of NaBH4 was added dropwise, and the resulting boiling mixture was further stirred for 3 hours. The starting rhodium compound. was decomposed and completely dissolved to give a uniform brown solution only. None of the desired compound was obtained. Comoarative Example 2 When the procedure of Comparative Example 1 was repeated except that starting materials, solvent and quantity of reducing agent were similar to those of Example 1(E), the starting rhodium.compound was decomposed and none of the desired compound was obtained. Comnarative Example 3 When the same procedure was repeated except that, in place of NaBH4 in Example 1(E), an aqueous solution of hydrazine in an equimolar quantity thereto was used, only RhCI(CO) (PPh3)2 was obtained through complete exchange of the ligand. Comoarative Example 4 0.45 g (0.490 mmol) of HRh(CO)(PPh3)3 and 0.173 g (equimolar thereto), 0.346 g (two times mol) or 1.73 g (ten times mol) of SbPh3 were added to 200 ml of ethanol and the resulting mixture was held for 1 hour at the boiling point of ethanol. In each case the starting rhodium compound was only decomposed and none of the compounds aimed at, respectively HRh(CO) (PPh3)2(SbPh3), HRh(CO) (PPh3) (SbPh3)2 and HRh(CO)(SbPh3)3 was obtained. Comoarative Example 5 When the procedure of Comparative Example 4 was repeated except that a temperature of 65 C was employed instead of the boiling temperature of ethanol and stirring continued for 4 hours, only the starting materials with some decomposed product were recovered, which compositions were not clear, and Wne desired compounds could not be obtained. ComParative Example 6 When the procedure of Example 1(G) was repeated except that RhCl(CO)(SbPh3)2 was used instead of RhI(CO)(SbPh3)2, only the starting materials were recovered. Comparative Example 7 0.130 g (0.498 mmol) of RhC13r3H20, 1.054 g. (corresponding to 6 times mol) of SbPh3 and 3 ml of an aqueous solution of formaldehyde were added to 150 ml of ethanol and the mixture was stirred at the boiling temperature of ethanol in a nitrogen atmosphere, to which mixture a solution of 0.188 g (4.95 mmol) of NaBH4 dissolved in ethanol was added dropwise, followed by refluxing for 3 hours. The starting rhodium compound was decomposed but no HRh(CO)(SbPh3)3 product was obtained. It will clearly be seen from a comparison of Example 1 with the Comparative Examples that the preparation process of the present invention is superior and commercially valuable. The novel rhodium compounds of the present invention are not only effective as a catalyst for the oxo reaction, but are also usable as a catalyst for the hydrogenation of unsaturated organic compounds, the isomerization of double bonds of olefins, the conversion of hydrogen to deuterium, hydrosilylation, and for various other uses. The advantages of the compounds of the present invention are illustrated by the use as a catalyst for the oxo reaction with propylene.as a raw material, the oxo reaction being carried out by the following procedure. Example 2 20 ml of n-dodecane and 0.109 mmol of a compound of the present invention prepared as described in Example 1 were charged to a 300 ml stainless steel autoclave, which was purged with nitrogen. 5.0 g (119 mmol) of propylene was introduced under pressure into the autoclave which was then heated to llO"C, an H2/CO gas with a molar ratio of 1/1 being introduced, and the reaction was carried out with the reaction pressure mainatained at 20 Kg/cmê. The time when the H2/CO gas was no longer absorbed was regarded as the final point of the reaction. After the reaction, the reaction product was subjected to analysis by gas chromatography, giving the results shown in Table 3. It is apparent from the results of Table 3 that the rhodium compound of the present invention is very effective as a catalyst for the oxo reaction. Table 3 Conversion Reaction Rate Reaction of Yield of n/i Ratio of Yield of Rhodium Compound -d(H2+CO)/dt Time Propylene Butylaldehyde Butylaldehyde Propane (ml/sec) (min) (mol %) (mol %) (mol %) HRh(CO)(AsPh3)(PPh3)2 13.5 13 90.8 89.8 2.0 0.7 HRh(CO)(SbPh3)(PPh3)2 1.5 100 43.0 42.1 1.9 0.4 HRh(CO)(PPh3)(AsPh3)2 10.2 30 89.5 88.6 2.1 0.6 HRh(CO)(SbPh3)(AsPh3)2 0.5 300 19.7 18.3 2.1 0.2 HRh(CO)(PPh3)(SbPh3)2 1.2 275 50.4 49.8 2.0 0.4 HRh(CO)(AsPh3)(AbPh3)2 0.4 300 17.7 16.8 2.2 0.3 HRh(CO)(SbPh3)3 0.2 300 7.5 7.0 2.3 0.3 Example 3 Example 2 was essentially followed with the modification that in addition to 0.109 mmol of the complex HRh(CO) (PPh3)2(AsPh3), triphenylphosphine and triphenylarsine were charged to the autoclave respectively in a proportion of 50 molts to 1 mol of the rhodium complex. The synthesis gas was continuously supplied from a gas holder to keep the reaction pressure constant. After the reaction had been continued for 22 minutes, from the start until the conversion of propylene reached approximately 90a, the autoclave was cooled rapidly and the product was withdrawn and subjected to analysis by gas chromatography. The reaction rate measured by the press sure decrease of the synthesis gas in the gas holder was 8.8 ml/sec. The conversion of propylene was 87.27. and the ratio of normal isomer to branched isomer was 3.7. The quantity of propane formed by the hydrogenation of the propylene was 0.4 mol 7.. Examoles 4 to 9 Hydroformylations using as catalyst the complexes HRh(CO) (PPh3)2(AsPh3) and HRh(CO)(PPh3)(AsPh3)2 prepared in Example 1 were carried out in a manner analogous to Example 3 but with variation of the quantity of excess ligands and reaction conditions, thus obtaining the results shown in Table 4. Comparative Examples 8 to 12 Hydroformylations using as catalyst the complex HRh(CO)(PPh3)3 synthesized in conventional manner were carried out in a manner analogous to Example 3 with change of conditions as shown in Table 4, thus obtaining the results shown therein. As can be seen from the Examples and the Comparative Examples, when an oxo reaction is carried out using as cata lust the complex containing mixed ligands and the excess mixed ligands, the reaction rate is increased to about 1.5 to 2 times as much as that obtained when using the complex containing phosphine only and the excess phosphine only, the nor mal chain to branched chain ratio of butylaldehyde is somewhat increased and the quantity of propane formed is somewhat decreased. Example 10 The hydroformylation reaction described in Example 3 was essentially repeated except that there was used as catalyst a still residue containing the rhodium catalyst and excess mixed ligands obtained by distilling the product of the hydroformylation reaction of Example 4 and separating the aldehyde. The results obtained are. shown in Table 4, from which 'it is apparent that the activity and selectivity are not changed and thus the catalyst can be reused even after - a heat treatment such as distillation. Example 11. The hydroformylation of Example 4 was repeated except that there was used a catalyst consisting of rhodium -supported on activated carbon (Rh content: 1.07. by weight) and excess mixed Ligands, thus obtaining the results shown in Table 4. Table 4 Reaction Butyl Rate aldehyde Rhodium PPh3/Rh AsPh3/Rh Reaction H2/CO -d(H2/ Propylene Normal/ Propane Ex. Complex Complex Complex Tempera- CO/dt Conversion Branched Yield No. (0.109 mmol) (mol ratio) (mol ratio) ture( C) (mol ratio) (ml/sec) (mol %) Ratio (mol%) 3 HRh(CO)PPh3)2 50 50 110 1.0 8.8 87.2 3.7 0.4 (AsPh3) 4 " 67 33 110 1.0 7.0 89.3 3.9 0.2 5 " 100 50 110 1.0 6.0 89.1 4.5 0.3 6 " 67 33 90 1.0 1.8 87.5 3.9 0.2 7 " 100 50 110 5.0 7.6 88.1 8.2 1.8 8 " 67 33 110 5.0 9.1 92.9 6.4 1.6 9 HRh(CO)(PPh3) 33 67 110 1.0 12.6 88.7 3.5 0.4 (AsPh3)2 8* HRh(CO)(PPh3)3 67 0 110 1.0 4.4 86.4 3.4 0.3 9* " 100 0 110 1.0 4.0 90.2 4.0 0.7 10* " 100 0 110 5.0 5.5 90.5 6.6 2.8 11* " 33 0 110 1.0 5.8 89.5 2.7 0.6 12* " 100 0 90 1.0 1.0 87.2 4.0 0.4 Catalyst of Ex. 4 - - 110 1.0 6.8 90.2 3.9 0.2 (reused) Rh/C (Rh 1.0 wt. %) 67 33 110 1.0 6.0 88.2 3.8 0.2 Note: Total Pressure = 20 Kg/cmê * = Comparative Example In another of its aspects, the present invention has advantages with regard to the ease of preparing or providing a rhodium-mixed ligands catalyst. The inventors have trade studies of a catalyst system consisting of an easily synthesizable or available rhodium source, for example, an inorganic rhodium compound such as rhodium metal or rhodium oxide, a rhodium organic sat such as rhodium acetate, or a rhodium complex such as rhodium carbonyl, Rh(CO)(Ph.3)2Ci or HRh(CO)(PPh3)3 and excess mixed ligands of a tertiary organo phosphorus and tertiary organo arsenic and have found that when hydroformylation is carried out with this catalyst system, the effect of hydroformylation is equal to that o the catalyst described in the foregoing. That is to say, the present invention relates to a process for producing aldehydes by reacting an olefin with carbon monoxide and hydrogen, the aldehydes having one more carbon atom than the olefin, which comprises carrying out the reaction in the presence of a rhodium source and free mixed ligands comprising a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula XR3 [wherein X' represents phosphorus or arsenic and R represents an organo group, which may be same or different) in excess of the quantity required for coordination to the rhodium atom. The easily obtainable or easily prepared rhodium source of the invention includes various rhodium compounds. Examples are a rhodium metal such as rhodium black or supported rhodium, an inorganic rhodium compound such as rhodium oxide, rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium bromide or rhodium iodide, a rhodium organic acid salt such as rhodium acetate or rhodium octoate, or a rhodium complex such as rhodium carboxyl, Rh(CO)2(acac), Rh(CO)(acac)(PPh3), Rh(CO)(PPh3)2Cl, [Rh(CO)2Cl]2, HRh(CO)(PPh3)3, HRh(CO)(AsPh3)3, HRh(CO)[P(OPh)3]3, Rh(acac)3, RhCl(PPh3)3, [RhCl(C2H4)2]2, [RhCl(1,5-COD)]2, Rh(CO)(AsPh3)2Cl, Rh(NO)(PPh3)3, [(1,5-COD)Rh(PPh3)2]ClO4 or [(l,5-COD)Rh(AsPh3)2) C104 (wherein acac X acetylacetonate, Ph = phenyl and COD = cyclo octadienyl). Preferred examples from the viewpoint of commercial availability and ease of preparation are complex compounds such as HRh(CO)(PPh3)3, HRh(CO)(AsPh3)3, Rh(CO)2(acac), [Rh(PPh3)]2, (Ph2PCH2Co2PPh2)2 ?nd HRh(CO) [P (OPh) The ligands (XR3) can have the general formula PR7R8R9 and As R10R11R12 in which R7 to R12 represent alkyl, cycloalkylt aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy, and aralkyloxy groups and may be the same or different. Preferably, R7, R8, R9, R1O, Rll and R12 are aryl groups and aryloxy groups and more preferably the same aryl group. In view of the reactivity and commercial availability, it is most preferably that they are all phenyl groups, that is, triphenyl phosphine and triphenyl arsine. The mixed ligands used in excess may be the same as or different from those contained in the rhodium complex, but the same ligands are advantageous commercially. The sum of the amounts of mixed ligands may be chosen within a wide range. In general, the sum of the amounts of free mixed ligands is 3 mols or more per rhodium atom in the rhodium source. Since addition of free mixed ligands in too large an excess is disadvantageous with respect to the reaction and cost, the excess amount is preferably 5 to 1000 mols, most preferably 50 to 500 mols per rhodium atom The proportion Of: tertiary organo phosphorus to tertiary organo arsenic used as mixed ligands in excess may be chosen within a wide range. This proportion is generally 5:1 to 1:5, preferably 2:1. to 1:3, in order to maintain the stability of the catalyst and show the effect of a mixed ligands system sufficiently. The above mentioned rhodium source and mixed ligands are provided in a hydroformylation reactor in order to carry out the hydroformylation but the rhodium source may be con tacted with a mixed gas of carbon monoxide and hydrogen in the presence of the mixed ligands in excess at an elevated pressure before the hydroformylation. In particular, a rhodium source containing halogen or rhodium nitrate is preferably treated with an alkaline reactant, e.g., aqueous sodium hydroxide, outside'the reaction system under the above mentioned conditions. It is known that the hydroformylation rate decreases with increasing mol ratio of a tertiary organo phosphorus to rhodium when carrying out the hydroformylation in the presence of a tertiary organo phosphorus-rhodium complex and a tertiary organo phosphorus in excess, see Journal of the Chemical Society (A) 1970, pp. 2753 - 2764. On the other hand, in a hydroformylation in the presence of a tertiary organo phosphorus-rhodium complex and a tertiary organo arsenic in excess, decrease of the reaction rate is observed too, with increasing moi ratio of a tertiary organo arsenic to rhodium, and moreover, the rate is extremely slow and the selectivity to normal aldehyde is low compared with that in the tertiary organo phosphorus in excess. The present invention shows the unique and co=er- dally valuable result, which comprises not slowing down the rate of hydroformylation and not lowering the selectivity to n-butylaldehyde caused by the presence of a tertiary organo arsenic in excess, but maintaining the selectivity to normalbutylaldehyde and improving the reaction rate to 1.5 to 2 times that of the known process using tertiary phosphorus liaands. The present invention provides a cotnmercialby valuable process whereby in the hydroformylation of olefins, the reaction rate is increased, the quantity of paraffin byproduct is decreased and, in addition, the selectivity to normal chain aldehyde is kept similar or improved in cpmpari- son with carrying out the reaction in the presence of a rhodium-tertiary organo phosphorus complex and excess tertiary organo phosphorus ligand in combination; and the greater ease of obtaining the catalyst and the similar effect on reaction rate, by-product and selectivity to normal aldehyde are shown in comparison with carrying out the reaction in the presence of a rhodium-tertiary organo phosphorus + tertiary organo arsenic complex and excess mixed ligands of tertiary organo phosphorus + tertiary organo arsenic ligand. The following examples are given in order to illustrate the present invention in detail without limiting the same . EXAMPLE 12 O.i09 mmol of tris (triphenyl phosphine) rhodium carbonyl hydride [HRh(CO)(PPh3)3], 3.60 mmon of triphenyl phosphine, 3.60 mmol of triphenylarsine and 20 ml of n-dodecane were charged toa 300 ml stainless steel autoclave equipped with a magnetic stirrer which was purged with nitrogen. 5.0 g of propylene was introduced under pressure into the autoclave which was then heated to 1100 C, an H2/CO gas with a molar ratio of L:1 was introduced and the reaction pressure was adjusted to 20 Kg/cm , followed by stirring. The synthesis gas was continuously supplied from a gas holder to keep the reaction pressure constant. After the reaction had been continued for 18 minutes, from the start until the conversion' of propylene reached about 90, the autoclave was cooled and the product was withdrawn and subjected to analysis by gas chromatography. The reaction rate measured by the pressure decrease of the synthesis gas in Ghe gas holder was 11.1 ml/ sec. The conversion of propylene was 89.37. and the ratio of normal isomer to branched isomer of butylaldehyde was 3.1. The yield of profane was 0.47o EXAMPLES 13 to 20 and COMPARATIVE EXAMPLES 13 to 18 Hydroformylations were carried out in a manner analogous to Example 12 except that the ratio of PPh3/rhodium and AsPh3/rhodium, reaction temperature and the mol ratio of H2/CO were varied, thus obtaining the results shown in the following Table 5. As can be seen from these results, in the catalyst system containing mixed excess PPh3 and AsPh3, the reaction rate is increased to about 1.5 to 2 times that in the catalyst system containing excess PPh3 only and the quantity of propane formed is somewhat decreased. EXAMPLE 21 and COMPARATIVE EXAMPLE 19 RhCl(CO)(AsPh3)2 which was synthesized from RhCl3#3H2O by the known method (L. Vallarince, J. Chem. Soc., (A) 2287 (1966)] was reacted in the presence of AsPh3 in excess, in ethanol solvent, and under a nitrogen atmosphere at 650C. After the reaction, the mixture was cooled to about OOC, and then an ethanol solution of NaBH4 was added dropwise, thereby forming HRh(CO)(AsPh3)3. Hydroformylations were carried out in a manner analogous to Example 12 except that the abo'7eentioned complex as rhodium source and mixed excess ligands of 5.45 mmol PPh3 and 5.45 mmol AsPh3 were used. The results are shown in Table 5 with the results of comparative Example 19 carried out in the presence of AsPh3 as the only excess ligand. It is apparent from these results that in a HRh(CO)(AsPh3)3/AsPh3 catalyst system, the activity and the selectivity to normal chain aldehyde are lower, but in a mixed ligands catalyst system, higher activity and higher selectivity are achieved EXAMPLE 22 Rh(CO)2(CH3CO CH2CO CH3) was svntnesized from [Rh(CO)2C1]2 by the known method [B.E. North et al. J. Organo metal Chem., 21 d45 (1970)]. Hydroformylations were carried out in a manner analogous to Example 12 except that this complex as rhodium source and mixed ligands of 5.45 mmol PPh3 and 5.45 mmol AsPh3 were used. The results are shown in Table 5. EXAMPLE 23 The hydroformylation of Example 12 was repeated except that a catalyst of rhodium-mixed ligands and excess mixed ligands was used. It is apparent from Table 5 that the other Examples and Example 23 show a similar effect on activity and selectivity to normal chain aldehyde. Table 5 Reaction Rhodium PPh3/Rh AsPh3/Rh AsPh3/ Reaction H2/CO Rate Source Source Source PPh3 Tempera- (mol -d(H2/CO)/dt No. (0.109 mmol) (mol ratio) (mol ratio) (mol ratio) ture( C) ratio) (ml/sec) Example 12 HRh(CO)(PPh3)3 33 33 1.0 110 1/1 11.1 13 " 33 67 2.0 " " 12.8 14 " 50 50 1.0 " " 8.4 15 " " 75 1.5 " " 8.6 16 " " 150 3.0 " " 6.9 17 " 100 50 0.5 " " 5.8 18 " " " " 100 " 3.2 19 " " " " 110 5/1 7.5 20 " 67 33 " " 1.0 4.4 Comparative Example 13 HRh(CO)(PPh3)3 33 - - 110 1/1 5.8 14 " 50 - - " " 5.6 15 " 100 - - " " 4.0 16 " 200 - - " " 2.5 17 " 100 - - 100 " 2.3 18 " 100 - - 110 5/1 5.5 Example 21 HRh(CO)(AsPh3)3 50 50 1.0 110 1/1 7.9 Comparative Example 19 " - " - " " 1.0 Example 22 Rh (CO)2(acac) 50 " 1.0 " " 7.6 Example 23 HRh(CO)(PPh3)2(AsPh3) 50 50 1.0 110 1/1 8.8 Table 5 (cont'd) n/i of Rhodium Propy- Butyl- Propane Source lene Conv. aldehyde Yield No. (0.109 mmol) (mol %) (mol ratio) (mol %) Example 12 HRh(CO)(PPh3)3 89.3 3.1 0.4 13 " 90.2 3.3 0.4 14 " 87.2 3.5 0.3 15 " 89.8 3.6 0.4 16 " 87.2 3.8 0.4 17 " 87.3 4.3 0.3 18 " 93.9 4.3 0.2 19 " 90.4 7.9 1.9 20 " 82.3 3.6 0.2 Comparative Example 13 HRh(CO)(PPh3)3 89.6 2.7 0.7 14 " 90.9 2.9 0.7 15 " 90.2 4.0 0.5 16 " 88.7 5.2 0.4 17 " 87.1 4.0 0.5 18 " 90.4 6.6 2.3 Example 21 HRh(CO)(AsPh3)3 90.7 3.3 0.3 Comparative Example 19 " 49.8 1.7 0.3 Example 22 Rh (CO)2(acac) 86.5 3.4 0.4 Example 23 HRh(CO)(PPh3)(AsPh3) 87.2 3.7 0.4

Claims: WHAT WE CLAIM IS: 1. A process for the production of aldehydes having one more carbon atom than the starting olefin by reacting the olefin with hydrogen and carbon monoxide, which comprises carrying out the reaction in the presence of a rhodium source and free mixed ligands comprising a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula X'R"3 [wherein X' represents phosphorus or arsenic and R" represents an organic group, which may be same or different) in excess of the quantity required for coordination to the rhodium atom. 2. A process according to claim 1 in which the rhodium source is selected from the group consisting of rhodium metal, an inorganic rhodium compound, a rhodium salt of an organic acid and a rhodium complex containing any of the following ligands: (a) CO (b) acetylacetonate (c) cyclooctadienyl (d) tertiary organo phosphorus (e) tertiary organo arsenic and mixtures of any of the above ligands. 3. A process according to claim 2 in which the rhodium source is selected from the group consisting of: HRh (CO)(PPh3)3 HRh(CO)(AsPh3)3 Rh(CO) 2(acac) [Rh(PPh3) 3] 2 PRh(Ph2PCR2CH2PPh2)2 XRh(CO)[P(oPh)3]3 4. A process according to claim 3 in which the rhodium source is HRh(CO)(PPh3)3. 5. A process according to claim 3 in which the rhodium source is HRh(CO)(AsPh3)3. 6. A process according to claim 1 in which the mixed ligands X R have the formula PR7R8Rg and AsRlORllRl2 in which R7 to R12 may be alkyl, cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy and aralkyloxy groups and may be the same or different 7. A process according to claim 6 in which R7 to R12 are aryl and/or aryloxy groups. 8. A process according to claim ] in which the mixed ligands are AsPh3 and PPh3. 9. A process according to claim 8 in which the AsPh3/PPh3 mol ratio is from 1:1 to 3:1. 10. A process according to claim 1 which comprises carrying out the reaction using a rhodium catalyst containing a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula, X'R"3 [wherein X' represents phosphorus or arsenic and R" represents an organic group7, and carbon monoxide in the presence of free mixed ligands comprising a tertiary organo phosphorus and tertiary organo arsenic represented by the general formula, X'R"3 " @@@ wherein X and R have the same meaning as above), in excess of the coordination quantity for rhodium. 11. A process according to claim 10 wherein there is used as catalyst under hydroformylation conditions a rhodium compound containing both a tertiary organo phosphorus ligand and'a:tertiary organo arsenic ligand and having the general formula HRh(CO) (ligand)3 in the presence of excess of mixed ligands of a tertiary organo phosphorus compound and a tertiary orga-no arsenic compound. 12. A process according to claim 11 wherein there is used as catalyst a rhodium complex having the general formula HRh(CO)(PR1RêR )n(AsR4R5R6)3-n in which R1,R2, R3, R4, -R5 and R6 are selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl and may be the same or different and n is 1 or 2, in the presence of excess mixed ligands of P and As having substituents selected from said group which may be the same as or different from those contained in the rhodium complex. 13. A process according to claims 1-12 in whiclr- the hydroformylation conditions comprise a temperature in the range of ambient to about 1500C., a total pressure in the range of atmospheric to about 100 atmospheres and a H2/CO mol ratio of 10/1 to 1/10. 14. A process according to claims 1-13 in which a solvent is present. 15. A process according to claim 14 in which the solvent is selected from the group consisting of saturated hydrocarbons, aromatic hydrocarbons, oxygen-containing compounds and hydroformylation products and by-products. 16. A process for the production of rhodium com pounds having the general formula: HRh(CO) (XR3)n(YR'3)3n in which X is phosphorus, arsenic or antimony; Y is arsenic or antimony when X is phosphorus, Y is phosphorus or antimony when X is arsenic or Y is phosphorus, arsenic or antimony when X is antimony; R and R' are aryl groups; and n is an integer of 1 or 2, which' comprises contacting a complex (a) represented by the general formula, RhZ(CO)(XR3)2 in which Z is a chloride (except when X and Y are both antimony), bromide or iodide anion with a ligand (b) repre sented by the general formula, YR'3 X, Y, R and R1 being as defined above, in a solvent, and adding a reducing agent comprising a hydride of a Group IIIA element at a temperature below room temperature, thereby reacting the mixture. 17. Rhodium compounds having the general formula, HRh(CO)(XR3)n(YR'3)3-n in which X is phosphorus, arsenic, or antimony; Y is arsenic or antimony when X is phosphorus, Y is phosphorus or antimony when X is arsenic, or Y is phosphorus, arsenic or antimony when X is antimony; R and R' are aryl groups and n is an integer of 1 or 2. 18. The compounds according to claim 17 having the formula: HRh(CO)(PR3)n(AsR'3)3-n. 19. The compounds according to claim 17 having the '; formula: HRh(CO) (PPh3)2(AsPh3). 20. The compounds according to claim having the formula: HRh(CO) (PPh3) (AsPh3) 2' 21. The compounds according to claim 17 having the formula: HRh(CO)(PR3)2(SbR'3). 22. The compounds according to claim 17 having the formula: HRh(CO)(PR3) (SbR'3). 23. The compounds according to claim 17 having the for=oula: HRh(CO)(AsR3)2(SbR'3). 24 . The compounds according to claim 17 having the formula: HRh(CO)(AsR3)(SbR'3)2. 25. The compounds according to claim 17 having the formula: HRh(CO) (SbR3)3.

Inventors: ISHII, YOSHIO, KANEKO, KATSUMI, MATSUSHIMA, YOSHIHISA, NAGASHIMA, YUKIO, OKAMOTO, NOBUKAZU, SAKAKIBARA, TADAMORI, WADA, SHOZO
Applicants: TOA NENRYO KOGYO K.K.
Application year: 1979
Main classification: C07C45
IPC codes: B01J31, C07C45, C07F15