Monovalent metal salts of dodecarhodiumtriaconta carbonyls
United States Patent 1191 Walker et al.  
 [ Apr. 15, 1975 MONOVALENT METAL SALTS OF DODECARHODIUMTRIACONTA CARBONYLS [75] Inventors: Wellington E. Walker, Charleston;  
 Earle S. Brown, S. Charleston; Roy L. Pruett, Charleston, all of W. Va.  
 [73] Assignee: Union Carbide Corporation, New  
 York, NY.  
  221 Filed: June 19, 1973 211 Appl. No.: 371,351  
 [52] U.S. Cl. 423/417 [5 1] Int. Cl C0lg 55/00; C01g 1/04 [58] Field of Search 423/249, 417, 418  
 [56] References Cited OTHER PUBLICATIONS Chini e t al, Synthesis of Rhodium Carbonyl Compounds at Atmospheric Pressure,&#34; Chemical Abstracts, Vol. 7], 1969, page 510 (56l8le).  
 Albano et al., Metal Atom Clusters in Polynuclear Carbmyl Compounds of Cobalt &amp; Rhodium, Chemical Abstracts, Vol. 71, 1969, pages 436 &amp; 437. Albano et al., Novel Metal Cluster in the Tetramethylammonium Salt of the Dioctahedral Themtacarbmyl Dodecarbodate Dianion [Rh, (CO) 1 Chemical Abstracts, Vol. 7l, page 376.  
 Primary Examiner-Earl C. Thomas Att0rney,&#39;Agent, or Firm-Michael L. Hendershot [57] ABSTRACT This invention relates to novel rhodium carbonyl metal salts having the formula 8 Claims, No Drawings MONOVALENT METAL SALTS OF DODECARHODIUMTRIACONTA CARBONYLS This invention is concerned with the formation of new rhodium carbonyl salts which are useful catalysts in the synthesis of reaction products of carbon monoxide and hydrogen.  
  The new rhodium carbonyl salts of this invention are characterized by the formula:  
 wherein M is a monovalent metal cation which is one of rhodium. copper. silver. gold. iridium. indium. and thallium.  
  The salts of this invention are believed to comprise a rhodium carbonyl&#39;cluster anion having the following structure:  
  This structure is believed to be readily ascertainable by infrared analysis which shows four (4) significant wave length bands in the metal carbonyl region in its infrared spectra at about 2070 cm. about 2045 cm. about 2008 cm and about 1773 cm. Each of these bands may vary by l5 cm&#34;&#39; The compositions of this invention &#39;can be prepared by the following enumerated processes:  
  I. These compositions may be prepared by contacting in an inert atmosphere tetrarhodium dodecacarbonyl with an excess of a soluble metal carboxylate of the desired metal cation in an appropriate solvent containing water in amounts up to 207: by weight of the solvent.  
  2. Alternatively. these compositions may be prepared by contacting under an atmosphere of carbon monox- .ide a monovale nt rhodium carbonyl cation complex with a soluble metal carboxylate in a suitable solvent containing water in amounts up to 20% by weight of the solvent.  
 3. These compositions can also be prepared via double decomposition ofan appropriate metal salt of dode-.  
 carhodium triacontacarbonyl anion. in which the metal cation is different from the desired metal cation. by contacting said salt with a salt of the desired metal. carrying out the double decomposition in an appropriate solvent under an inert atmosphere.  
  It is believed that the above processes are achieving part or all of the reactions in the sequence depicted below:  
  For example. in the case of the first enumerated process. the first step of the process is believed to be that depicted as (b) followed by reactions (c) through (g). In the case of the second enumerated process. the first step is believed to be that depicted as (a) followed by reactions (b) through (g). In the case of the third enumerated process. the reaction involves only l t2 .&#39;tul  
  ln reaction (a) above. L can be the anions of strong mineral acids (Cl. SO PQ-C. NO;f and the like). carboxylates. and organic ligands such as compounds which contain at least I nitrogen atom (hereinafter called Lewis base nitrogen atom) and/or at least I oxygen atotn (hereafter called Lewis base oxygen atotn said atoms possessing a pair of electrons available for the formation of coordinate bonds with rhodium. Desirably. the organic ligand contains at least 2 Lewis base nitrogen atoms. or at least 2 Lewis base oxygen atoms. or at least 1 Lewis base nitrogen atom plus at least 1 Lewis base oxygen atom. said atoms possessing a pair of electrons available for the formation of coordinate bonds with rhodium. and said organic ligand forming with rhodium per se a chelate structure. In suitable embodiments the organic ligands contain from 2 and upwards to 4 Lewis base atoms. preferably from 2 to 3 such atoms. and most preferably 2 Lewis base atoms. These organic ligands are said to be multiden tate or polydentate. that is to say. such ligands are bidentate. tridentate. or quadridentate. depending on whether 2. 3. or 4 Lewis base atoms are involved in the formations of chelate structures with rhodium.  
  Organic ligands which contain at least one Lewis base nitrogen atom will oftentimes hereinafter be referred to as organic nitrogen ligands&#34;: those ligands which contain at least l Lewis base oxygen atom will oftentimes be referred to as organic oxygen ligands&#34;: and those which contain at least 1 Lewis base nitrogen atom plus at least 1 Lewis base oxygen atom will oftentimes be referred to as organic aza-oxa ligands&#34;.  
  Suitable organic nitrogen ligands most generally contain carbon. hydrogen. and nitrogen atoms. Suitable organic oxygen ligands most generally contain carbon. hydrogen. and oxygen atoms. Suitable organic aza-oxa ligands most generally contain carbon. hydrogen. oxygen. and nitrogen atoms. The carbon atoms can be acyclic and/or cyclic such as aliphatic. cycloaliphatic. aromatic (including fused and bridged) carbon atoms. and  
 the like. Preferably. the organic ligands contain from 2 to 20 carbon atoms. The nitrogen atoms can be in the form of imino (N=). amino nitrilo (N i etc. Desirably. the Lewis base nitrogen atoms are in the form of imino nitrogen and/or amino nitrogen. The oxygen atoms can be in the form of groups such as hydroxyl (aliphatic or phenolic). carboxvl R (-COH),  
 carbonyloxy methyl ester of ethylenediaminetetraacetic acid. and oxy (-O). carbonyl the like.  
  Other organic compounds which form ionic associa- 9 tion with rhodium carbonyl compounds are useful li- (-C-), gands. They are from organic compounds which possess Lewis base nitrogen atoms and typically are cometc.. all of said groups containing Lewis base oxygen Posed of Cllrbm1- y and nitrogen lustrmbe of atoms. In this respect. it is the hydroxyl&#39; oxygen in the Such cumpllunds 1lrc- -gplperidinemethylpiperidine. 3-methylpiperidine. pyridine. 2- Q methylpyridine. 4-ethylpiperidine. dibutylamine. m- ...(;0 thylamine. dodecylamine. morpholine. aniline. benzyl- I amine. octadecylamine. naphthylamine. cyclohexylgroup and the oxyoxygen in the umlncand the The enumerated processes can be operated at tem- Q I5 peratures ranging from about 0 to about 375C. and preferably at ambient room temperature (about 2()28C.) up to about 100C. The pressures employed group that are the Lewis base awn The Organic are dependent upon the amount of carbon monoxide gands may also contain other atoms and/or groups such mqu&#39;red m complete pmduct fmmuuon&#39; the as alkyl. cycloalkyl. aryl. chloro. thiaalkyl. trialkylsilyl. F emlmflatgd r Carbon monoude pleshure and thc km is not required. therefore the process can be carried out at atmospheric pressure or under superatmospheric pressure. The second enumerated process requires carbon monoxide pressure since reaction (a) requires CO 35 addition.  
  The residence time of the reactions can be followed by taking periodic infrared sprectra of samples of the reaction. The reaction time varies with the process chosen. the pressures employed. the temperatures used. and the like considerations.  
  The inert atmosphere is any gaseous material which does not interfere with the reaction(s). and. c.g.. includes nitrogen. argon. helium. krypton. neon. and the Illustrative organic nitrogen ligands include for instance. N.N.N.N-tetramethylethylenediamine. N.N.- N&#39;.N&#39;-tetraethylethylenediamine. N.N.N&#39;.N&#39;-tetra-npropylethylenediamine. N.N.N&#39;.N&#39;-tetramethylmethylencdiamine. N.N .N &#39;.l\&#39; &#39;-tetraethylmethylenediamine. N.N.N.N&#39;-tetraisobutylmethylenediamine. piperazine. N-methylpiperazine. N-ethylpiperazine. Z-methyl-N-methylpiperazine. 2.2&#39;-dipyridyl. methylsubstituted 2.2&#39;-dipyridyl. ethyl-substituted 2.2- dipyridyl. 1.4-diazabicyclo [2.2.2]octane. methylsubstituted l.-l-diazabicyclo [2.2.2]octane. purine. 2-  
 aminopyridinc. Z-(dimethylamino)pyridine. l.l()- like ni i m pw nwthyl-sugsnit.utmtjh 2 In the practice of these processes. the solvents emp E T T. 7 hl l &#39;d i i ployable include. by way of example: iiwi q i if g i i i saturated and aromatic hydrocarbons. e.g.. hexane. mu 1mm) MPH) octane. dodecane. naphtha. decalin. tetrahydrophenanthroline. and the like.  
  Illustrative organic oxygen ligands include. by way of 40 illustrations. glycolic acid. methoxyacetic acid. ethoxnaphthalene. kerosene. mineral oil. cyclohexane. cycloheptane. alkylcycloalkane. benzene. toluene. xylene. naphthalene. alkylnaphthalene. etc; others such yacetic acid. diglycolic acid. thiodiglycollc acid. dlethyl us tetrahydmfumm tetrahydmpymm diethyl ether ether. tetrahydrot uran. d oxane. tetrahydropyran. pydimelhoxybcnzeng Llethoxybenzene the mono and mcmechol Clmc dialkyl ethers ofethylene glycol. ofpropylene glycol. of ethoxyethanol. Z-n-propoxyethanol. Z-n-butylethanol. butflene gIWOL of (ethylene glycol of dipropvlene f Y Y l lb glycol. of dibutylene glycol. of triethyleneglycol. 0f tet- 2.3-dlhydroxynaphthalene. cyclohexane-l.2-dtol. oxemethyleneglywL of (yethyleneoxypmpylene glycol I-2&#39;dlmelhml&#39;benzfint l-zdlethoxl&#39;benzena ctc.; alkanols such as methanol. ethanol. propanol. isomethyl acetate. ethanol. l.Z-dmtethoxyethane. 1.2- bumnol LethvlhexanOL ketones Such as acetone diethmlvcthlmfi- &#39;P p y methyl ethyl ketone. cyclohexanone. cyclopentanonc. butoxyethane. pentane-l-l-dione. hexane-2.4-dione. esters Such as methyl acewm ethyl acetam prom. heptane-3.5-dione. octane-l-l-dione. l-phenylbutaneacetate -1 fleeting mflhyl propionme ethyl b l.3-dione. 3-methylpentane-2.4-dione; the monoand h l l rate, etc.; water; anhydrides such as dialkyl P fi l&#39; of diethylcme gIYCOL phthalic anhydride. acetic anhydride. etc.&#39;. and others.  
 &#34; p py l 11nd tht? like Tetrahydrofuran. dioxane. and the mono and dialklllustratire organic aza-oxa ligands include. for examl h f i h l d tetmethylene l l are ple. ethanolamine. diethanolamine. isopropanolamine. f d di] m di-n-propanolamine. N-N-dimethylglycine. N.N- The following procedures represent the best modes diethylglycine. iminodiacetic acid. N- available for producing the salt products of this invenmethyliminodiacetic acid. N-methyldiethanolamine. tion as depicted in the table below: Z-hydroxypyridine. methyl-substituted 2- hydroxypyridine. picolinic acid. methyl-substituted pic- PROCEDURE A olinic acid. nitrilotriacetic acid. 2.5-dicarboxypipera- Tetrarhodium dodecacarbonyl (0.13 mol) is charged zine. N-(Z-hydroxyethyl)iminodiacetic acid. ethyleneto a glass vessel equipped with a magnetic stirrer bar diaminetetraacetic acid. 2.6-dicarboxypyridine. 8- along with a mono alent metal cation carboxylate (2.5 hydroxyquinoline. 2-carboxyquinoline. cyclohexanemol) and an appropriate solvent such as tetrahydrol.2-diamine-N.N.N.N&#39;-tetraacetic acid. the tetrafuran containing water in an amount up to 20% by weight of the solvent. These reagents are stirred under a neutral atmosphere. The reaction is followed by periodic determination of the infrared spectrum of the mixture.  
 PROCEDURE B To a clean. dry saponification kettle containing a magnetic stirrer bar. is added under a nitrogen purge bis(carbonyl) (acetylacetonato) rhodium (l) (2.7-1 g. 0.0105 mol.), the metal carboxylate (0.05 mole). and tetrahydrofuran which is freshly distilled from lithium is consistent with the presence of the cluster anion |2 :m  
 PROCEDURE C TABLE Monovalent Metal Salt Reaction Time, Procedure Salt Product Hours Employed Cu C]. 3 C Cu [Rh (CO) Ag N 2 C Ag [Rh (CO) 1 Inc 2 C In [Rh12(C0) m1 oocclt 24 A TJL [Rh (C0) I 0 l [amcm m c1 5 c Rh(co) z Rh (C0) [Mtge] C aluminum hydride (80 ml.). The bottle is sealed employing a neoprene septum and perforated bottle cap. To the mixture is then added 0.4 ml. of distilled water via syringe. The bottle is then purged thoroughly with carbon monoxide and 26 psig CO is applied to the bottle via a syringe needle coupled to a pressure bottle of CO. The contents are stirred at room temperature for the periods oftime specified below. The pressure bottle is depressurized and placed in a glove box under N. The reactor contents. deep violet in color. are discharged and are filtered to remove excess metal carboxylate. The resulting solution is concentrated by evaporation of tetrahydrofuran. Deep violet crystals of M [R (CO); are then recovered. lts infrared spectrum both as a mull and in solution in tetrahydrofuran What is claimed is: l. Rhodium carbonyl metal salts of the formula zl ut Otml wherein M is a monovalent metal cation selected from the group consisting of rhodium. copper. silver. gold.  
  iridium. indium and thallium.  
 2. The salt of claim 1 wherein M is rhodium. 3. The salt of claim 1 wherein M is copper. 4. The salt of claim 1 wherein M is silver.  
 5. The salt of claim 1 wherein M is gold.  
 6. The salt of claim 1 wherein M is iridium. 7. The salt of claim 1 wherein M is indium. 8. The salt of claim 1 wherein M is thallium.  
  UNITED STATES PATENT omen CERTIFICATE OF CORRECTION Patent No. 357 3292 ssue Date April 15, 1975 a l Inventor(s) W. E Walker, E Brown, R. L, Pruett It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 k cgtumrl r ilne D4 at Grant, Page 4, (d) of application: I 9 snoutd be replaced with a bracket, to close the bracketed matter.  
  Signed and Scaled this twenty-fourth Day of February 1976 [SEAL] Arrest:  
 RUTH C. MASON C. MARSHALL DANN Allesting Officer Commissioner ufParenrs and Trademarks