United States Patent (19) 11) 4,288,634 Sakakibara Et Al
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United States Patent (19) 11) 4,288,634 Sakakibara et al. 45) Sep. 8, 1981 (54) NOVEL RHODIUM COMPOUNDS AND 1357735 6/1974 United Kingdom......... 260/604 HF PROCESS FOR PRODUCING THE SAME 1440413 6/1976 United Kingdom ......... 260/604 HF (75) Inventors: Tadamori Sakakibara; Yoshihisa OTHER PUBLICATIONS Matsushima; Yukio Nagashima; Nobukazu Okamoto; Katsumi Catalyst Reviews, vol. 6(1), pp. 66–83, (1972). Kaneko, all of Ooi; Yohio Ishii, J. of Synthetic Organic Chemistry (Japan), vol. 35, (8), Nagoya; Shozo Wada, Zushi, all of pp. 683-688, (1977). Japan Hydrocarbon Processing, vol. 6, pp. 83-91, (1975). Chem. Eng. vol. 26, p. 109, Dec. 5, 1977. 73) Assignee: Toa Nenryo Kogyo Kabushiki Kaisha, Tokyo, Japan Primary Examiner-Werren B. Lone Attorney, Agent, or Firm-Rebecca Yablonsky (21) Appl. No.: 73,664 (57) ABSTRACT 22 Filed: Sep. 7, 1979 This invention relates to rhodium compounds having 30 Foreign Application Priority Data the general formula: Apr. 10, 1978 JP Japan ................................ 53/121456 Apr. 10, 1978 JP Japan ................................ 53/121457 51) Int. Cl. .............................................. C07C 45/50 (52) U.S. Cl. .................................................... 568/454 wherein X is phosphorus, arsenic or antimony; Y is 58) Field of Search ......................................... 568/454 arsenic or antimony when X is phosphorus, Y is phos (56) , References Cited phorus or antimony when X is arsenic, or Y is phospho rus, arsenic or antimony when X is antimony; R and R' U.S. PATENT DOCUMENTS are aryl groups; and n is an integer of 1 or 2. Further, it 3,168,553 2/1965 Slaugh .......................... 260/604 HF relates to a process for the preparation of aldehydes by 3,487, 12 6/1969 Paulik et al. ................. 260/604 HF the hydroformylation of olefins in the presence of a 3,527,809 9/1970 Pruett et al. ... 260/604 HF rhodium catalyst, and more particularly for the produc 3,821,311 6/1974 Hughes ....... 260/604 HF 3,857,900 12/1974 Wilkinson ... ... 252/431 tion of aldehydes by the reaction of olefins such as 3,954,877 5/1976 Gipson ... ... 260/604 HF propylene with carbon monoxide and hydrogen in the 4,052,461 10/1977 Tinker .......................... 260/604 HF presence of HRh(CO)(PPh3)2(AsPh3)/excess PPh3 and 4,148,830 4/1979 Pruett ........................... 260/604 HF AsPh3 or HRh(CO)(PPh3)(AsPh3)2/excess PPh3 and AsPh3. FOREIGN PATENT DOCUMENTS 129833l 11/1972 United Kingdom ......... 260/604 HF 5 Claims, 2 Drawing Figures 2005 200 995 1985 1980 Sum of the Pauling electro-negativities (Xp) U.S. Patent sep. 8, 1981 Sheet 1 of 2 4,288,634 F.G. 1930 1920 90 1880 1870 Sum of the Pauling electro-negativities (Xp) U.S. Patent Sep. 8, 1981 Sheet 2 of 2 4,288,634 FIG. 2 2005 2000 1995 1985 1980 Sum of the Pauling electro-negativities (Xp) 4,288,634 1. 2 compounds, it has been proposed to add to a binuclear NOVEL RHODIUM COMPOUNDS AND PROCESS rhodium compound (RhCl(CO)L)2 wherein L is tri FOR PRODUCING THE SAME phenylphosphine, triphenylarsine or triphenylstibine in warm benzene an ether solution of 2 mols (equimolar BACKGROUND OF THE INVENTION 5 amount) of L being triphenylphosphine, triphenylar 1. Field of the Invention sine or triphenylstibine but not the same as L (Journal of This invention relates to new rhodium compounds Organometallic Chemistry, Vol.43, No. 2, 1972, page and a process for producing the same. More particu 425). larly, it is concerned with new rhodium compounds Other references of lesser interest, noted because they having a structure isoelectronic to HRh(CO)(PPh3)3 10 concern rhodium-containing compounds, are U.S. Pat. and a process for the selective production of the same. Nos. 3,939,188 and 3,946,082, which relate to com Further, it relates to use of such products as catalysts in pounds containing reduced, Zero valent rhodium and the oxo process. U.S. Pat. No. 4,052,461 which relates to ionic rhodium 2. Description of the Prior Art compounds but not the hydrides which are nonionic. Carbonyl tris (triphenylphosphine) rhodium hydride 15 However, mixed ligands-containing rhodium com is known as a catalyst having activity in various chemi pounds having a structure isoelectronic to cal reactions for organic syntheses, for example, in hy HRh(CO)(PPh3)3 or three stibines-coordinated rho droformylation. (Japanese Patent Publication No. dium compounds cannot be obtained, or mixtures of 10730/1970 equivalent to U.S. Pat. No. 3,527,809). See various rhodium compounds are only obtained, by the also U.S. Pat. No. 3,821,311 and Canadian Pat. No. 20 above described method or other known methods and it 992,101. As rhodium compounds having a structure is very difficult to isolate such compounds in a pure isoelectronic thereto are known carbonyl tris(triphenyl form. phosphite) rhodium hydride HRh(CO)(P(OPh)3)3 (Brit Rhodium-phosphine type or rhodium-phosphite type ish Pat. No. 1338225), carbonyl tris(triphenylarsine) complexes are known as catalysts for the hydroformyla rhodium hydride HRh(CO)(AsPh3)3 and carbonyl tris 25 (triphenylarsite) rhodium hydride HRh(CO)(As tion of olefins. The stability of a rhodium catalyst is (OPh)3)3 (British Pat. No. 1357735). As to producing increased by modification with phosphine, arsine, or these compounds, some processes are known. In the stibine, which permits practicing the oxo reaction at a case of HRh(CO)(PPh3)3, for example, there have been rather low pressure. proposed (1) a process comprising reacting rhodium 30 According to Japanese Pat. No. 903,326, straight trichloride. trihydrate, excess triphenylphosphine, an chain-rich aldehydes are prepared at a low total pres aqueous solution of formaldehyde and sodium borohy sure with a low partial pressure of carbon monoxide and dride in boiling ethanol (Journal of the Chemical Soci a high partial pressure of hydrogen in the presence of a ety (A), 1968, page 2660), (2) a process comprising rhodium triarylphosphine catalyst and a triarylphos reacting carbonyl bis(triphenylphosphine) rhodium 35 phine ligand in a large exess to the rhodium. However, chloride, excess triphenylphosphine and sodium boro this method has the disadvantage that the hydroformy hydride in boiling ethanol (ibid) and (3) a process com lation reaction rate of an olefin is markedly decreased prising contacting carbonyl bis(triphenylphosphine) because of using a ligand in a large excess to rhodium, rhodium chloride and excess triphenylphosphine with and a considerable quantity of a paraffin is formed by synthesis gas (mixture of H2 and CO) at a temperature of 40 the hydrogenation of the olefin ("Hydrocarbon Pro at least 55 C. under a pressure of at least 10 atm. (Japa cessing” (4) 112 (1970) due to the reaction at a low total nese Patent Publication No. 17572/1978). pressure with a low partial pressure of carbon monoxide However, carbonyl tris(triphenylstibine) rhodium and a high partial pressure of hydrogen. hydride HRh(CO)(SbFh3)3 having a structure isoelec Rhodium catalysts in combination with arsines or tronic to the above described rhodium compounds has 45 stibines instead of phosphines have been proposed, but not been synthesized and isolated. Moreover, as is evi the studies thereof have not been made so intensively dent from the foregoing description, all the rhodium because of their lower activity compared with tertiary compounds having the above described known struc phosphine-rhodium catalysts. tures contain respectively a single kind of ligand and SUMMARY OF THE INVENTION those containing different kinds of mixed ligands, for 50 example, phosphines and arsines in the same molecule, Applicants have made various efforts to obtain new are not known, although some monovalent rhodium rhodium compounds having a structure isoelectronic to compounds containing mixed ligands in the same mole HRh(CO) (PPh3)3 and, as a result, have succeeded in cule are known, for example, carbonyl triphenylphos obtaining new rhodium compounds represented by the phine triphenylarsine rhodium chloride 55 following general formula in high yield and in a pure RhCl(CO)(PPh3) (AsPh3) (Journal of Organometallic form, thus accomplishing the present invention. It is Chemistry, Vol. 43, No. 2, 1972, page 425), carbonyl estimated that in the new compounds the rhodium is triphenylphosphine triphenylstibine rhodium chloride mono-valent. This invention further relates to a process RhCl(CO)(PPh3)(SbFh3) (ibid), carbonyl triphenylar for the production of aldehydes by the hydroformyla sine triphenylstibine rhodium chloride RhCl(CO)- 60 tion of olefins and more particularly, it is concerned (AsPh3)(SbFh3) (ibid) and carbonyl (diethylphenyl with an improved process for producing aldehydes by phosphine) (tri-o-toluylstibine) rhodium chloride reacting olefins, carbon monoxide and hydrogen in the RhCl(CO)(PPhEt2)(Sb(o-CH2C6H4)3) (Inorganic presence of rhodium-containing complex compound Chemistry, Vol. 15, No. 13, 1976, page 646). See also J. catalysts and free ligands. That is to say, the gist of the Chem. Soc. D1970, (17), 1077-8 (England); Inorg. 65 present invention consists in novel rhodium compounds Nucl. Chem. Lett. 1971, 7(9)877–9 (England); J. Chem. represented by the general formula, Soc. Dalton Trans. 1972 (19) 2161-9 (England) and U.S. Pat. No. 3,459,780. As a method for synthesizing these 4,288,634 3 4. (V) HRh(CO)(ASR3)2(SbR's) wherein X is phosphorus, arsenic or antimony; Y is (VI) HRh(CO)(AsR3)(Sbr') arsenic or antimony when X is phosphorus, Y is phos (VII) HRh(CO)(SbR) phorus or antimony when X is arsenic or Y is phospho (R and R' have the same meanings as described rus, arsenic or antimony when X is antimony; R and R' 5 above.) are aryl groups, which may be the same or different; Useful examples of these compounds, in particular and n is an integer of 1 or 2, and a process for their where R and R' are the same and are phenyl groups, are production.