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United States Patent 0 ICE Patented Apr , 3,378,569 United States Patent 0 ICE Patented Apr. 16, 1 968 1 2 mium tricarbonyl, diphenyl methane molybdenum tricar 3,378,569 ARENE METAL CARBONYLS bonyl, and diphenyl methane tungsten tricarbonyl. Roy L. Pruett, Charleston, and John E. Wym'an, St. Al Alkoxy substituted compounds such as anisole chro bans, W. Va., and Donald R. Rink and Leo Parts, Buf mium tricarbonyl, phenetole chromium tricarbonyl, 1,3 falo, N.Y., assignors to Union Carbide Corporation, a dimethoxybenzene chromium tricarbonyl, anisole molyb corporation of New York denum tricarbonyl, and anisole tungsten tricarbonyl. No Drawing. Filed Sept. 12, 1958, Ser. No. 760,558 Aryloxy substituted compounds such as diphenyl ether 5 Claims. (Cl. 260-3403) chromium tricarbonyl, 1,3-diphenoxybenzene chromium tricarbonyl, 1,4-diphenoxybenzene chromium tricarbonyl, This invention relates to organo-metallic carbonyls. diphenyl ether molybdenum tricarbonyl, and diphenyl More particularly, this invention relates to arene metal ether tungsten tricarbonyl. carbonyls wherein the metal is chromium, molybdenum Alkenyl substituted compounds such as allylbenzene or tungsten. chromium tricarbonyl, styrene chromium tricarbonyl, Bis(arene)organo-metallic compounds in which two alphamethylstyrene chromium tricarbonyl, allylbenzene aromatic hydrocarbon groups are bonded to each metal molybdenum tricarbonyl and allylbenzene tungsten tri~ atom, for example bis(benzene)chromium and bis(ben carbonyl. zene)molybdenum, have been described. Such compounds Alkhydroxy substituted compounds such as benzyl al and a method for their preparation are disclosed in sev cohol chromium tricarbonyl, beta~phenyl ethyl alcohol eral published articles by E. O. Fischer and coworkers. chromium tricarbonyl, beta-B-tolylethyl alcohol chromi See, for example, Z. Naturforshung, 10(b), 665 (1955); 20 um tricarbonyl, benzyl alcohol molybdenum tricarbonyl, Chem. and Ind, 1956, 153; Z Anorg. Allgem. Chem, and benzyl alcohol tungsten tricarbonyl. 286, 142 (1956); ibid., p. 146; Ber., 89, 1805 (1956); Hydroxyl substituted compounds such as phenol chro ibid., p. 1809; and Angew. Chem, 68, 462 (1956). The mium tricarbonyl, resorcinol chromium tricarbonyl, organic groups of the bis(arene)metal compounds of the phloroglucinol chromium tricarbonyl., phenol molyb published articles include only hydrocarbon groups, such denum tricarbonyl, and phenol tungsten tricarbonyl. as benzene, mesitylene and tetrahydronaphthalene. Amino substituted compounds such as aniline chro We have now discovered a new and useful class of or mium tricarbonyl, p-phenylene diamine chromium tricar gano~metallic compounds wherein only one arene organic bonyl, 1,3,5-triaminobenzene chromium tricarbonyl, ani group is bonded to each metal atom and wherein the line molybdenum tricarbonyl, and aniline tungsten tri arene organic group may contain any of a wide variety 30 carbonyl. of chemical elements and functional groups. N-alkylamino substituted compounds such as N-methyl These novel organo-metallic compounds are arene aniline chromium tricarbonyl, N-ethylaniline chromium metal carbonyls, for example benzene chromium tricar tricarbonyl, N-n-butylaniline chromium tricarbonyl, N bonyl. methylaniline molybdenum tricarbonyl, and N-methylani We have further discovered a. process by which the or line tungsten tricarbonyl. gano-metallic compounds of this invention may be N,N-dialkylamino substituted compounds such as N,N produced. dimethylaniline chromium tricarbonyl, N,N-diethylaniline The compounds of this invention may be represented chromium tricarbonyl, N,N~di-n-butylaniline chromium by the formula tricarbonyl, N,N-dimethylaniline molybdenum tricar ArM(CO)3 bonyl, and N,N-dirnethylaniline tungsten tricarbonyl. where M is selected from the group consisting of chro Halogeno substituted compounds such as chlorobenzene mium, molybdenum and tungsten and Ar is an arene chromium tricarbonyl, bromobenzene chromium tricar organic compound containing the benzenoid ring system. bonyl, iodobenzene chromium tricarbonyl, ?uorobenzene The benzenoid ring system is the six~carbon, unsaturated chromium tricarbonyl, chlorobenzene molybdenum tri ring which may be represented by the structural formula carbonyl, and chlorobenzene tungsten tricarbonyl. Aldehydo substituted compounds such as benzaldehyde chromium tricarbonyl, o-methylbenzaldehyde chromium tricarbonyl, p-methylbenzaldehyde chromium tricarbonyl, benzaldehyde molybdenum tricarbonyl, and benzaldehyde 50 tungsten tricarbonyl. I Nitro substituted compounds such as nitrobenzene chromium tricarbonyl, m-dinitrobenzene chromium tri The simplest members of the class of compounds rep carbonyl, rn-nitrotoluene chromium tricarbonyl, nitro resented by the above formula are benzene chromium benzene molybdenum tricarbonyl, and nitrobenzene tung tricarbonyl, benzene molybdenum tricarbonyl and ben 55 sten tricarbonyl. zeue tungsten tricarbonyl. Additional examples’ of com Cyano substituted compounds such as benzonitrile pounds of this invention which illustrate the above for chromium tricarbonyl, 4-cyanobiphenyl chromium tri mula are the following: carbonyl, o-dicyanobenzene chromium tricarbonyl, benzo~ Alltyl substituted compounds such as toluene chromium nitrile molybdenum tricarbonyl, and benzonitrile tungsten tricarbonyl, mesitylene chromium tricarbonyl, cumene 60 tricarbonyl. chromium tricarbonyl, toluene molybdenum tricarbonyl, Acyl substituted compounds such as acetophenone toluene tungsten tricarbonyl, 9,10-dihydroanthrocene chromium tricarbonyl, benzophenone chromium tricar chromium tricarbonyl, and hexamethyl benzene chromium bonyl, propiophenone chromium tricarbonyl, aceto tricarbonyl. phenone molybdenum tricarbonyl, and acetophenone tung Aryl substituted compounds such as biphenyl chromi 65 sten tricarbonyl. um tricarbonyl, terphenyl chromium tricarbonyl, quater Sulfhydryl substituted compounds such as benzenethiol phenyl chromium tricarbonyl, biphenyl molybdenum tri chromium tricarbonyl, o-methyl sulfhydrylbenzene chro carbonyl, biphenyl tungsten tricarbonyl, and alpha mium tricarbonyl, p~methylsulfhydrylbenzene chromium naphthyl benzene chromium tricarbonyl. tricarbonyl, benzenethiol molybdenum tricarbonyl, and Aralkyl substituted compounds such as diphenyl 70 benzenethiol tungsten tricarbonyl. methane chromium tricarbonyl, alpha~naphthyl phenyl Alkylsulfonyl substituted compounds such as methyl methane chromium tricarbonyl, diphenyl ethane chro sulfonyl-benzene chromium tricarbonyl, ethylsulfonyl 8,378,569 3 4 benzene chromium tricarbonyl, propylsulfonylbenzene The organo-metallic compounds of the present inven chromium tricarbonyl, methylsulfonylbenzene molybde tion may be characterized as addition compounds in con num tricarbonyl, and methylsulfonylbenzene tungsten tri trast to organo-metallic substitution compounds. In the carbonyl. latter, a hydrogen or other substituent in the organic Arylsulfonyl substituted compounds such as benzenesul nucleus is substituted or removed in the formation of the fonyl benzene chromium tricarbonyl, p-diphenylsulfonyl organometallic compound. However, no hydrogen, alkyl benzene chromium tricarbonyl, o-tolylsulfonylbenzene or other substituent is removed from or replaced on the chromium tricarbonyl, benzene suifonyl benzene molybde arene organic moiety in the formation of the arene metal num tricarbonyl, and benzenesulfonyl benzene tungsten carbonyls of this invention. tricarbonyl. 10 The compounds of this invention should be distin Carboalkoxy substituted compounds such as carbo guished from addition compounds such as the hexa methoxybenzene chromium tricarbonyl, carbcethoxy pyridine chromium cation, Cr(NC5I-I5)6+3, wherein benzene chromium tricarbonyl, dibutylphthalate chromi~ bonding between the metal and the organic group re um tricarbonyl, carbomethoxybenzene molybdenum tri— sults from a conventional covalent (two electron) bond carbonyl, and carbomethoxybenzene tungsten tricarbonyl. between the metal atom and one other atom in the or Carboxamido substituted compounds such as benz ganic group. amide chromium tricarbonyl, N-methylbenzamide chro According to the process for producing the compounds mium tricarbonyl, o-toluamide chromium tricarbonyl, of this invention, an arene organic compound and a metal benzamide molybdenum tricarbonyl, and benzamide tung carbonyl are reacted either in solution or in the vapor sten tricarbonyl. phase. This process may be represented by the equation Carboxyl substituted compounds such as benzoic acid chromium tricarbonyl, phthalic acid chromium tricar bonyl, toluic acid chromium tricarbonyl, benzoic acid or, representing the arene organic group in more detail, molybdenum tricarbonyl, and benzoic acid tungsten tri by the equation carbonyl. Sulfonamido substituted compounds such as benzene sulfonamide chromium tricarbonyl, o-methylbenzenesul~ fonamide chromium tricarbonyl, p~methy1benzenesul fonamide chromium tricarbonyl, benzenesulfonamide molybdenum tricarbonyl, and benzencsulfonamide tung 30 stcn tricarbonyl. Benzene rings substituted with mixed substituents such wherein Ar, M and R have the meanings de?ned herein as alkyl, alkoxy benzene: for example, anethole, may also above. form the compounds of this invention. Still other ex The embodiment of the process wherein the reaction amples are p-cresol chromium tricarbonyl, salicylaldehyde ' takes place in the vapor phase may be conveniently chromium tricarbonyl, anisaldehyde chromium tricar carried out by passing vapors of metal carbonyl and arene bonyl, m-nitroaniline chromium tricarbonyl,
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