2,870,180 United States Patent Office Patented Jan. 20, 1959 1. value of from 0 to 2 inclusive, and the sum a--b-c-d--f 2,870,180 has a value of from 3 to 15 inclusive. PROCESS FOR THE PREPARATION OF HYDRO Thus, our invention includes a process for the syn SEES MANGANESE CARBONY, COM thesis of compounds having the general formula P D 5 RMn(CO) John Kozikowski and Melvin L. Larson, Royal Oak, comprising reacting a manganese compound having the Mich, assignors to Ethyl Corporation, New York, general formula N.Y., a corporation of Delaware RMnR No Drawing. Application October 13, 1955 10 with a metal carbonylic compound having the general Serial No. 540,348 formula 4 Claims. (C. 260-429) (CO) wherein M is a metal selected from a group consisting of This invention relates to a process for the synthesis 5 groups VI-B, VII-B and VIII of the periodic table and of hydrocarbon manganese carbonyl compounds. In having atomic numbers within the range of from 24 to particular, this invention relates to a process for the 78, wherein a has a numerical value of from 1 to 4 in synthesis of cyclopentadienyl-type manganese tricarbonyl clusive and b has a numerical value of from 3 to 12 in compounds hereinafter called cyclomatic manganese tri clusive. Examples of the metal carbonylic compounds carbonyl compounds. 20 are Fe(CO)5, Co(CO)3)4, and ERh4(CO)11). The A novel type of cyclomatic manganese tricarbonyl com above is a case where, in the general formula pound in which the manganese is bonded to an organic or hydrocarbon radical by a carbon-to-manganese bond through carbons which form part of a five-membered c=d=f-0. This is the preferred method of carrying out cyclopentadienyl-type ring have been recently discovered. 25 the synthesis of the cyclopentadienyl-type manganese tri These compounds have been found to be useful as addi carbonyl compounds. Of the metal carbonyls, the group tives to lubricating oils and hydrocarbon fuels for the VIII metal carbonyls, such as Fe(CO)5, are preferred. purpose of improving their lubricating and combustion Our invention also includes the process for making properties, as well as for other uses. The discovery of compounds having the general formula RMn(CO) com these new compounds has disclosed a need for a suitable 30 prising reacting a manganese compound having the general method of synthesizing them. formula It is therefore an object of our invention to provide a process for the preparation of cyclopentadienyl-type with a metal carbonylic compound having the general manganese tricarbonyl compounds. It is also an object formula of this invention to provide a process for the synthesis 35 of cyclopentadienyl-type manganese tricarbonyl com M(CO).X.H. pounds which can be conducted at low or atmospheric wherein M is a metal chosen from a group consisting of pressures. Another object of this invention is to provide groups I-B, VII-B and VIII of the periodic table, having a method for the synthesis of cyclomatic manganese tri atomic numbers within the range of from 25 to 79, where carbonyl compounds which utilizes readily available car 40 in a has a numerical value of 1 to 2 inclusive, b has a bon monoxide donors. Additional objects of this in numerical value of from 1 to 5 inclusive, c has a numerical vention will become apparent from the discussion which value of from 1 to 3 inclusive, and f has a numerical follows. value of from 0 to 1 inclusive. Examples of these metal The above and other objects of this invention are carbonylic compounds are Re(CO)5Br, HPt(CO) accomplished by a process for the preparation of hydro 45 and Au(CO)Cl. This is a case where, in the general carbon cyclomatic manganese tricarbonyl compounds formula Mn(CO)XRH, the letter d=0. having the general formula Our invention likewise includes a process for the prepa RMn(CO) ration of compounds having the general formula wherein R is a cyclomatic hydrocarbon radical having 50 RMn(CO) 5 to 17 carbon atoms which embodies a group of five carbons having the general configuration found in cyclo comprising reacting a manganese compound having the pentadiene, said compounds being further characterized general formula in that the cyclomatic hydrocarbon radical is bonded to RMnR' the manganese by carbon-to-manganese bonds through 55 the carbons comprising the cyclopentadienyl-group con with a metal carbonylic compound having the general figuration, comprising reacting a manganese compound formula having the general formula M(CO)H, 60 wherein M is a metal selected from the group consisting wherein R and R' have the composition defined for R of groups VII-B and VIII of the periodic table having above, with a metal carbonylic compound having the atomic numbers within the range of from 25 to 77, and general formula wherein a has a numerical value of 1, b has a numerical value of from 4 to 5 inclusive, and f has a numerical value 65 of from 1 to 2 inclusive. Examples of these metal car wherein M is a metal having an atomic number of from bonylic compounds are HRe(CO)5 and HIr(CO). This 23 to 79, selected from groups I-B, V-B, VI-B, VII-B is a case where, in the general formula M(CO).X.R.H., and VIII; X is a halogen having an atomic number of c=d=0 from 9 to 53; R is as defined above; a is a number from Our invention also includes a process for the manufac 1 to 4 inclusive; b is a number from 1 to 12 inclusive; c. ture of compounds having the general formula has a numerical value of from 0 to 3 inclusive; d has a 70 numerical value of from 0 to 1 inclusive; if has a numerical RMn(CO) 2,870,180 3 4. comprising reacting a manganese compound having the as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, general formula sec-butyl, t-butyl, n-amyl, the various positional isomers RMR' thereof as, for example, 2-methylbutyl; 1,1-dimethyl propyl; 1-ethylpropyl, and the corresponding straight and with a metal carbonylic compound having the general branched chain isomers of hexyl, heptyl, octyl, nonyl, formula decyl, undecyl, dodecyl, tetradecyl, hexadecyl, nondecyl, M(CO)RHy eicosyl and the like. Likewise, the univalent aliphatic wherein M is a metal selected from the group consisting substituent can be an alkenyl radical, Such as ethenyl, of groups V-B, VI-B and VIII of the periodic table, hav Al-propenyl, A-propenyl, isopropenyl, A-butenyl, A-bu ing atomic numbers within the range of from 23 to 78, 0 tenyl, A3-butenyl, and the branched chain isomers thereof and wherein a has a numerical value of 1, b has a nu as A-butenyl, A2-isobutenyl, A-sec-butenyl, Al-Sec-bu merical value of from 2 to 4 inclusive, d has a numerical tenyl, Al-pentenyl, A-pentenyl, and the branched chain value of 1, and f has a numerical value of 0 to 1 inclusive. isomers thereof A1-hexenyl, A3-hexenyl, A-hexenyl, and Examples of metal carbonylic compounds of this kind the branched chain isomers thereof, including 3,3-di are (CH)V(CO)4 and (CH)Pt(CO)H. This is a case methyl-A1-butenyl; 2,3-dimethyl-A-butenyl, and 1-methyl where, in the general formula Ma (CO) bXRHf, C has 1-ethyl-A-propenyl, and the various isomers of heptenyl, a numerical value of Zero. octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetra An example of the process of this invention is the re decenyl, heptadecenyl, octodecenyl, eicosenyl, and the like. action of bis(cyclopentadienyl)manganese with iron penta When the organic radical substituted in the cyclomatic carbonyl to give cyclopentadienyl manganese tricarbonyl. 20 group is a univalent aliphatic radical, it can be an aralkyl Other examples are given hereinbelow. radical such as, for example, benzyl, a-phenylethyl, Our process has the advantages of low pressure op B-phenylethyl, c-phenylpropyl, a-phenylisopropyl, o-phen erability and high yield of the desired RMn(CO)3 prod ylbutyl, o-phenylisobutyl, 6-phenyl-tert-butyl, o'-naphthyl ucts. An additional advantage is the production of valu methyl, B'-naphthylmethyl, ox-(o'-naphthyl)propyl, ox-((3'- able by-products. naphthyl)isopropyl, y - (o'-naphthyl) butyl, ox-(o'-naph The reaction can be carried out in either the con thyl)isobutyl, 6-(6'-naphthyl)-sec-butyl, the correspond densed phase or the vapor phase. It is preferred, how ing ox’- and (3'-naphthyl derivatives of n-amyl and the ever, to carry out the reaction in the condensed phase, various positional isomers thereof, and the like. Other utilizing low pressure equipment. An advantage to a such aralkyl radicals include the ox'-, ps'-, and y-anthryl condensed phase reaction is that it can be carried out at 30 derivatives of alkyl radicals such as o'-anthrylmethyl, a lower temperature, since it is not necessary to heat f3-(y'-anthryl)ethyl, A-(6'-anthryl)-2-methylamyl, and the the reagents to vaporization temperature. It is especially like, and the corresponding alkyl derivatives of phenan prepared to react metal carbonylic compounds with cyclo threne, fluorene, acenaphthene, chrysene, pyrene, triphen pentadienyl-type manganese compounds in the liquid me ylene, naphthacene, etc. The univalent aliphatic radical dium in which the cyclomatic manganese compounds 35 can be an aralkenyl radical such as o-phenylethenyl, were prepared. An example of this is the preparation B-phenylethenyl, cy-phenyl-Al-propenyl, and the phenyl of bis(methylcyclopentadienyl)manganese by the reaction derivatives of the isomers of butenyl, pentenyl, heptenyl, of methylcyclopentadienyl sodium with manganous chlo and the like, up to about eicosenyl. Other such aryl ride in an ether solution, such as tetrahydrofuran, and alkenyls include o-(c.'-naphthyl)-ethenyl, a-(6'-naphthyl)- the addition of iron pentacarbonyl to the reaction mixture 40 ethenyl, ox-(o'-naphthyl)-Al-propenyl, a-(o'-naphthyl)-A- at temperatures within the range of 0 to 103° C. to pro propenyl, ox-((3'-naphthyl)-isopropenyl, and the like. In duce methylcyclopentadienyl manganese tricarbonyl. addition, such aromatic derivatives of alkenyls, that is, Our process is especially preferred for the synthesis of aralkenyl radicals, include derivatives of phenanthrene, compounds in which at least one of the carbon-to-carbon fluorene, acenaphthene, chrysene, naphthacene, and the double bonds in the cyclopentadienyl-group configuration like. is olefinic in nature. In other words, in this preferred When the organic radicals comprising the substituents embodiment not more than two carbons of the cyclo in the cyclomatic groups are univalent alicyclic radicals, pentadienyl ring should be shared with a fused aromatic these can be radicals selected from the group consisting ring such as a benzene ring. An example of one of the of cycloalkyl and cycloalkenyl radicals. Thus, such uni cyclomatic radicals of this preferred embodiment is the 50 valent alicyclic radicals can be cycloalkyl radicals such indenyl radical as, for example, cyclopropyl, cyclobutyl, cycloamyl, cyclo hexyl, cyclononyl, cycloadecyl, cyclododecyl, cycloocto decyl, cycloeicosyl, and such cycloaliphatic radicals as o-cyclopropylethyl, ox-cyclobutylpropyl, and the like. 55 Similarly, the alicyclic radical substituents can be cyclo alkenyl radicals such as ox-cyclohexylethenyl, a -cyclo H heptyl-Al-propenyl, B-cyclooctyl-A-propenyl, ox-methyl When R and R', the cyclomatic radicals, have this type ene-6-cyclododecylethyl, and the like. of configuration or structure, that is, where at least one When the organic radicals substituted in the cyclomatic double bond in the cyclopentadienyl-group configuration 60 groups of the compounds made by our process are uni is olefinic, the resulting cyclomatic manganese compounds valent aromatic radicals, they can be selected from the are found to have the optimum characteristics for use group consisting of aryl and alkaryl radicals. Thus, these as fuel and lubricating oil additives. univalent aromatic radicals can be aryl radicals such as, The cyclopentadienyl part of the molecules prepared for example, phenyl, naphthyl, anthryl, and the like, in by our invention consist of a cyclopentadienyl nucleus, cluding the various monovalent radicals of such aromatics the carbon skeleton of which can have other organic or as indene, acenaphthene, fluorene, naphthacene, chrysene, hydrocarbon substituents thereon having up to 12 or more and the like. Moreover, these univalent aromatic radi carbon atoms. cals can be alkaryl radicals such as, for example, tolyl, When a cyclomatic radical of the compounds prepared 3,5-xylyl, p-cumenyl, mesity, ethylphenyl, 2-methyl-o- by the process of our invention is substituted with uni naphthyl, 1-ethyl-6-naphthyl, and the like. valent aliphatic radicals, these substituents can be radicals Having amply described the meaning of the term “or having from 1 to about 12 or more carbon atoms, se ganic radical,” the discussion with regard to cyclomatic lected from the group consisting of alkyl, alkenyl, aralkyl radicals has been facilitated. As stated hereinabove, the and aralkenyl. Thus, when these substituents are uni cyclomatic groups of the compounds of the present in valent aliphatic radicals, they can be alkyl radicals, such 75 vention can be represented by four general formulae. 2,870,180 5 6 The first class of cyclomatic radicals can be represented The same discussion applies to each of the carbon atoms by the general formula designated as 4 and 5 when b is zero. Illustrative ex R3 R4 amples of this type of cyclomatic radical include 4,5,6,7- tetrahydroindenyi; 1,2,3,4,5,6,7,8-octahydrofluorenyl; 3 5 methyl-4,5,6,7-tetrahydroindenyl, and the like. . Non-limiting examples of the compounds prepared by R. Y (I) the process of our invention in which the cyclomatic radi wherein each of R, R2, R3, R4 and Rs can be the same cal has the configuration shown in Structure I above are or different and is selected from the group consisting of cyclopentadienyl manganese tricarbonyl; methylcyclopen hydrogen and organic or hydrocarbon radicals having () tadienyl manganese tricarbonyl; ethylcyclopentadienyl from about 1 to about 12 or more carbon atoms. Illus manganese tricarbonyl; propylcyclopentadienyl manga trative examples of such cyclomatic radicals include cy nese tricarbonyl; butenylcyclopentadienyl manganese tri clopentadienyl; methylcyclopentadienyl; 1,2-dimethylcy carbonyl; tert-butylcyclopentadienyl manganese tricar clopentadienyl; ethylcyclopentadienyl; 1,3,4-tripropylcy bonyl; hexylcyclopentadienyl manganese tricarbonyl; clopentadienyl; 1,5-diphenylcyclopentadienyl; 1-methyl cyclohexylcyclopentadienyl manganese tricarbonyl; hep 3-tert-butylcyclopentadienyl; isopropenylcyclopentadienyl; tylcyclopentadienyl manganese tricarbonyl; decylcyclo 1,2-di(A-isobutenyl)-cyclopentadienyl; 1-methyl-3-(Ai pentadienyl manganese tricarbonyl; dodecylcyclopentadi pentenyl)-cyclopentadienyl; (6-phenylethyl)-cyclopenta enyl manganese tricarbonyl; 1,2,3,4-tetramethylcyclopen dienyl; cyclohexylcyclopentadienyl; phenylcyclopentadi tadienyl manganese tricarbonyl; 1,2,3,4,5-pentamethyl 20 cyclopentadienyl manganese tricarbonyl; 1,3-dibutylcyclo enyl; 1-ethyl-3-(o-methyl)-cyclopentadienyl; (o-tolyl)- pentadienyl manganese tricarbonyl; 1,2-dipropyl-3-cyclo cyclopentadienyl; acetylcyclopentadienyl, and the like. hexylcyclopentadienyl manganese tricarbonyl; tolylcyclo The second type of cyclomatic radical is the indenyl pentadienyl manganese tricarbonyl; 1,3-diphenylcyclopen type radical represented by the general formula tadienyl manganese tricarbonyl; acetylcyclopentadienyl R4 25 manganese tricarbonyl, and the like. R3 Rs When there is only one organo or hydrocarbon sub stituent on the cyclopentadienyl ring, its position is not R2 R specified since, according to theory, the cyclopentadienyl R ring or group is bonded to the manganese by five equiv R Y (II 30 alent bonds running from each of the five carbons in the wherein each of R1, R2, R3, RA, R5, R6 and R can be cyclopentadienyl ring to the manganese. Since all these the same or different and is selected from the group con bonds are equivalent and all five carbons in the ring are sisting of hydrogen and organic and hydrocarbon radicals equidistant from the manganese, it is immaterial to which having from 1 to about 12 or more carbon atoms. Illus of the five carbons a single substituent is attached. When, trative examples of such cyclomatic radicals include however, more than one substituent is attached to the indenyl; 2-methylindenyl; 1-sec-butylindenyl; 3,4-di cyclopentadienyl ring, the positions are given so as to indi ethenylindenyl; 5-(a-phenylbutyl)-indenyl; 1-cyclohexyl cate the relative positions of the different substituents with indenyl; 1-phenylindenyi; 4,5-diphenylindenyl, and the respect to each other on the cyclopentadienyl ring. like. Examples of compounds having the configuration of The third type of cyclomatic radical is a radical of the 40 Structure II given hereinabove are indenyl manganese tri fluorenyl type which can be represented by the general carbonyl; 3-methylindenyl manganese tricarbonyl; 3 formula ethenylindenyl manganese tricarbonyi; 2,3-dimethylin denyl manganese tricarbonyl; 1,3-diethylindenyl manga nese tricarbonyl; 1,7-diisopropylindenyl manganese tri carbonyl; 1,2,3,4,5,6,7-heptamethylindenyl manganese tri carbonyl; 5-phenylindenyl manganese tricarbonyl; 3 (2- ethylphenyl)indenyl manganese tricarbonyl, etc. Examples of compounds having the configuration of (III) Structure III above are fluorenyl manganese tricarbonyl; wherein each of R1, R2, R3, R4, R5, R6, R, R8 and Rg 3-ethylfluorenyl manganese tricarbonyl: 4-propylfluo can be the same or different and is selected from the renyl manganese tricarbonyl; 2,3,4,7-tetramethylfluorenyl group consisting of hydrogen and organic and hydrocar manganese tricarbonyl, and the like. bon radicals having from 1 to about 12 or more carbon Examples of compounds having the cofinguration of atoms. Illustrative examples of such radicals include Structure IV above are 4,5,6,7-tetrahydroindenyl manga fluorenyl; 3-ethylfluorenyl; 4,5-dipropylfluorenyl; 9-meth nese tricarbonyl; 3-methyl-4,7-dihydroindenyl manganese ylfluorenyl; 6-ethenylfluorenyl; 4-benzylfluorenyl; 2-m- tricarbonyl; 2 - ethyl-3-phenyl - 4,5,6,7- tetrahydroin tolylfluorenyl, and the like. denyl manganese tricarbonyl; 1,2,3,4,5,6,7,8-octahydro The fourth type of cyclomatic radical, that is, a radical fluorenyl manganese tricarbonyl; 1,4,5,8-tetrahydrofluo containing the cyclopentadienyl moiety can be represented renyl manganese tricarbonyl, and the like. by the general formula 60 The cyclopentadienyl-type manganese compounds that are employed in this process, as stated hereinabove, have 3 4 the general formula RMnR. Non-limiting examples of (CH2). (CH2) these cyclopentadienyl manganese compounds are bis 2 5 (cyclopentadienyl)manganese; cyclopentadienyl-methyl cyclopentadienyl manganese; bis(methylcyclopentadi (IV) enyl)manganese; bis(ethylcyclopentadienyl)manganese; wherein a and b can be the same or different and are bis(amylcyclopentadienyl)manganese; ethylcyclopentadi small whole integers including zero and excluding one, enyl-amylcyclopentadienyl manganese; bis(phenylcyclo the sum a--b being at least two, and wherein R is pentadienyl)manganese; bis(dodecylcyclopentadienyl)- selected from the class consisting of hydrogen and or manganese; 1,3,5-trimethylcyclopentadienyl)manganese; ganic radicals. Thus, when a is zero, each of the carbon bis(indenyl)manganese; bis(tetrahydroindenyl)manga atoms designated as 2 and 3 have attached thereto a nese; bis(6-methylindenyl)manganese; cyclopentadienyl monovalent radical selected from the class consisting of indenyl manganese; bis(1-cyclohexylindenyl)manganese; hydrogen and organic radicals. Furthermore, the mono bis(fluorenyl)manganese; methylcyclopentadienyl-fluo valent radicals so attached can be the same or different. 75 renyl manganese; indenyl-fluorenyl manganese; bis(6- 2,870,180 7 8 ethenylfluorenyl)manganese; bis(4-benzyl)fluorenyl man Moeller, 1952 edition, published by John Wiley and Sons. ganese; bis(1,2,3,4,5,6,7,8-octahydrofluorenyl)manganese. The cyclopentadienyl metal carbonyl compounds used in The metal carbonylic compounds employed in this our process are made by reacting the cyclopentadienyl proceSS are metal carbonyls, metal carbonyl halides, metal metal compound with carbon monoxide at elevated pres carbonyl hydrides, cyclomatic carbonylic compounds, and 5 Sures. For example, the reaction of bis(cyclopentadienyl) cyclomatic metal carbonyl hydrides composed of metals chromium with carbon monoxide and hydrogen under of groups I-B, V-B, VI-B, VII-B and VIII of the periodic pressures of up to 200 atmospheres produces cyclopenta table. For example, we can employ the group I-B car dienyl chromium tricarbonyl hydride which melts with bonyl halide compounds such as Cu(CO)Cl. Likewise, the evolution of hydrogen to form cyclopentadienyl we can employ the cyclopentadienyl group V-B metal car O chromium tricarbonyl. Another method is the reaction of bonyl compounds such as, for example, (CH)V(CO)4. metal carbonyl halide with an alkali metal derivative of We can also employ the group VB-I metal carbonyls and the cyclopentadienyl compound to produce the cyclo cyclomatic group VI-B metal carbonyl hydrides as, for pentadienyl metal halide. example, Cr(CO)6 and indenyl tungsten tricarbonyl hy The general method of preparation of cyclopentadienyl dride. Among the metal carbonylic compounds we can 5 type manganese tricarbonyl compounds, according to this employ are included the group VII-B metal carbonyls as invention, is the reaction of cyclopentadienyl-type man well as halide and hydride derivatives thereof as, for ex ganese compounds with metal carbonylic compounds. ample, Mn(CO)5, Re(CO)5Br and HRe(CO). We also AS Stated hereinabove, the process can be carried out employ the carbonylic derivatives of the group VIII either in the vapor phase or the condensed phase. The metals which include the metal carbonyls, the metal car 20 following examples serve to illustrate our process. bonyl halides, metal carbonyl hydrides, and the cyclo matic metal carbonylic compounds, as well as cyclomatic Example I metal carbonyl hydrides and cyclomatic metal carbonyl halides, such as Fe(CO), (CH)Ni(CO)H, etc. Fur CYCLOPENTADIENYL MANGANESE TRICARBONYL ther non-limiting examples of these compounds are: 25 A reaction vessel equipped with means for charging and discharging liquids and solids, gas inlet and outlet METAL CARBONYLS means, temperature measuring devices, heating and cool Cr(CO) Ru(CO)4 ing means, means for agitation, and means for condens Mo(CO) Os(CO) ing vapors was flushed with pre-purified nitrogen. To W(CO) Os(CO)2 30 the flask were then added 400 parts of tetrahydrofuran Mn(CO)5] Co(CO)4 and 23 parts of sodium dispersed in 23 parts of mineral Re(CO)5] Co(CO)4 oil. An atmosphere of nitrogen was maintained in the Fe(CO)5 IRh(CO)4 reaction vessel throughout the run. To the vessel was Fe(CO) IRh(CO)3] added 66.7 parts of freshly-distilled cyclopentadiene in Fe(CO)4 Rh4(CO)11m 35 Small increments with agitation while maintaining the Ru(CO)5 Ir(CO)4 temperature below 40 C. over a period of about two Ru(CO) Ir(CO) hours, when the completion of the formation of the so Ni(CO) dium cyclopentadiene was evidenced by the cessation of METAL CARBONYL HALDES hydrogen evolution. To this solution of cyclopentadi 40 enyl Sodium in tetrahydrofuran was added 63 parts of Mn(CO)5X Co(CO)I. anhydrous manganous chloride. The mixture was heated Re(CO)X Rh(CO)2X and maintained at reflux temperature for 20 hours. At Fe(CO)5X Ir(CO)X the end of this time, the solvent was removed by distilla Fe(CO)4X Ir(CO)2X tion under reduced pressure and the product purified by Fe(CO)Bra Pd(CO)Cl. Sublimation at a pressure of about 2 mm. of mercury at Fe(CO)2X HIPd(CO)Cl. about 130° C. producing 48.64 parts, 52.5% yield, of Fe(CO)I Pt(CO)Cl. lustrous, brown-black bis(cyclopentadienyl)manganese Ru(CO)2X Pt(CO)X. crystals. The product was kept under an atmosphere of Ru(CO)Br HIPt(CO)X nitrogen to prevent oxidation by oxygen of the air. Os(CO)4X Cu(CO)X To 46 parts of bis(cyclopentadienyl)manganese crys Os(CO)3X Ag(CO)Cl. tals in a reaction vessel equipped with temperature con Os(CO)2X Au(CO)Cl. trol means and means for refluxing liquids is slowly IOs (CO) XI. added 85 parts of iron pentacarbonyl at a temperature X-F, Cl, Br or I of Substantially 20 C. The temperature of the reaction METAL CARBONYL HYDRDES 5 s mixture is then slowly raised to 100° C. and maintained HMn(CO) HCo(CO) at that level for a period of about 20 hours. The reac HRe(CO) HRh(CO) tion between bis(cyclopentadienyl)manganese and iron H2Fe(CO)4 HIr(CO) pentacarbonyl produces cyclopentadienyl manganese tri HOs (CO)4 etc. carbonyl, dicyclopentadienyl diron tetracarbonyl, dicyclo (30 pentadienyl iron and Small amounts of other cyclopenta CYCLOPENTADIENYL-TYPE METAL dienyl carbonyl derivatives of manganese and iron. The CARBONY LIC COMPOUNDS products are separated by fractional distillation and sub limation at reduced pressure. The cyclopentadienyl manganese tricarbonyl is a yellow, air-stable, water-in I, Soluble Solid having a melting point of 77° C. and corre sponds to the formula (C5H5)Mn(CO)3. The dicyclo pentadienyl diron tetracarbonyl, (C5H5)2Fe(CO)4, has a melting point of 194° C. and the bis(cyclopentadienyl) iron melts at 173-74 C. In these compounds (CH) represents a cyclopentadienyl () A good yield is also obtained when the reaction of group, (CH) a methylcyclopentadienyl group and Example I between bis(cyclopentadienyl)manganese and (CH) an indenyl group. Other carbonylic compounds iron pentacarbonyl is carried out at a temperature of 20° that can be used are those of the metals Nb, Tc and Ta. C. The reaction is also found to proceed at a tempera The methods for the preparation of various metal car ture as low is 0° C. to give the product cyclopentadienyl bonylic compounds is found in Inorganic Chemistry by 75 manganese tricarbonyl. 2,870,180 10 Example II C. The combined stream of bis(methylcyclopentadienyl)- Bis(methylcyclopentadienyl)manganese was prepared manganese and the iron carbonyl is admitted into the re in a manner similar to the preparation of bis(cyclopenta action vessel below the surface of the ether. The ether dienyl)manganese in Example I, except that the Serves as a reaction and heat transfer medium in which bis(methylcyclopentadienyl)manganese was not separated 5 the manganese compound and the iron carbonyl react to from the reaction product. Iron pentacarbonyl was for methylcyclopentadienyl manganese tricarbonyl, added directly to the reaction mixture containing the bis(methylcyclopentadienyl)manganese and further reac (CH)Mn(CO) tion allowed to proceed at a temperature of substanitally and by-products of iron, such as bis(methylcyclopenta 80 C. to produce methylcyclopentadienyl manganese O dienyl)iron and dimethylcyclopentadienyl diron tetra tricarbonyl which is purified by fractional distillation at carbonyl. The methylcyclopentadienyl manganese tri reduced pressures. The product is a yellow-orange carbonyl product is separated from the reaction mixture liquid having a freezing point of -0.75 C., a refractive by fractional distillation in good yield. index (n) of 1.5873 and a density (d) of 1.3942. A variation of the procedure in Example VII com On analysis the compound is found to correspond to the prises passing a stream of nitrogen or other inert gas formula (C6H)Mn(CO)3. The by-products are di(meth through the bis(methylcyclopentadienyl)manganese com ylcyclopentadienyl)diron tetracarbonyl, pound as the latter is being vaporized. The inert nitro gen gas serves as a carrier for transporting the manganese compound to the reaction vessel where it reacts with the and bis(methylcyclopentadienyl)iron, (CH)2Fe. 20 iron carbonyl compound. An inert carrier gas can be Similar results are obtained when a mixture of cyclo likewise employed to aid in the transportation of the iron pentadiene and methylcyclopentadiene are employed, pentacarbonyl vapors to the reaction vessel. Other in producing a product consisting of a mixture of cyclo ert gases employed with equal Success are argon, helium, pentadienyl manganese tricarbonyl and methylcyclopenta methane, ethane, etc. The requirement with respect to dienyl manganese tricarbonyl. 25 the characteristics of the carrier gas is that it does not re When Re(CO)3Cl is used in place of Fe(CO) in Ex act with either the reagents or the product which is ob ample II, a good yield of methylcyclopentadienyl man tained when the manganese compound and the carbonylic compound react. Similar results are obtained when other ganese tricarbonyl is likewise obtained. cyclomatic manganese compounds and other metal car Example III 30 bonylic compounds of the type named hereinabove are The process of Example II is repeated employing employed. ethylcyclopentadiene as the cyclomatic compound and The vapors of the cyclomatic manganese compounds dicyclopentadienyl diiron tetracarbonyl as the carbonyl and the metal carbonylic compounds can also be passed donor. The reaction is carried out at 223 C. in butyl into the reaction Zone maintained at a suitable reaction o-tolyl ether in place of tetrahydrofuran. The product 35 temperature which is below the decomposition point of obtained is ethylcyclopentadienyl manganese tricarbonyl. the reactants and the two compounds allowed to react without the presence of a liquid medium. The products Example IV of the type obtained in Example VII are produced. An Employing the process of Example II with phenyl example of this is the reaction of bis(methylcyclopenta cyclopentadiene as the cyclomatic compound, nickel tetra 40. dienyl)-manganese with iron pentacarbonyl in the vapor carbonyl as the carbonyl donor and a mixture of toluene state in a reaction Zone at temperatures of substantially and dioxane as the solvent, a good yield of phenylcyclo 110 C. in the presence of nitrogen gas as an inert car pentadienyl manganese tricarbonyl is obtained when the rier. This method is not quite as efficient as the reaction reaction is conducted at temperatures within the range of the vapors below the surface of a liquid medium and of 20-90° C. smaller yields of the desired product are obtained. Similar results are obtained when Co(CO)4 is used Whether the process is carried out in a gaseous medium in place of Ni(CO)4. or in a liquid medium, the unreacted vapors of the cyclo matic manganese compound and the metallic carbonylic Example V compound can be recycled. Mediums other than alkyl Employing bis(indenyl)manganese and cyclopenta 50 tolyl ether and nitrogen gas can be used as described more dienyl vanadium tetracarbonyl as reactants in ethylene fully hereinbelow. glycol diethyl ether in a process as described in Example As stated above, our invention comprises reacting cy I, in which the reaction is conducted at temperatures of clopentadienyl-type manganese compounds with metal car substantially 170° C., indenyl manganese tricarbonyl is bonylic compounds to produce cyclopentadienyl-type man obtained as the product. 55 ganese tricarbonyl compounds. The bis(cyclopentadienyl When Ru(CO)5 is used in place of cyclopentadienyl type) manganese compounds can be prepared in a number vanadium tetracarbonyl and the process of Example V of ways. One method comprises reacting manganese salt, carried out at a temperature of 250 C., a good yield such as manganous chloride, with a cyclopentadienyl-type of indenyl manganese tricarbonyl is likewise obtained. alkali metal compound. This method is illustrated in 60 Example I. Another method of preparing bis(cyclo Example VI pentadienyl-type) manganese compounds is the reaction of The reaction of bis(fluorenyl)manganese with cyclo a cyclopentadienyl magnesium halide-known as a Grig pentadienyl chromium tricarbonyl hydride in ally tolyl nard reagent-with a manganese Salt, such as a man ether produces fluorenyl manganese tricarbonyl. ganous halide. An example of the latter is the reaction In similar manner, bis(2-ethyl-3-naphthylcyclopenta 5 of manganous chloride with cyclopentadienyl magnesium dienyl)manganese reacts with copper carbonyl iodide, chloride in an ether Solvent to produce bis(cyclopenta CuCOI, in a medium of benzene and ethyl ether to pro dienyl)manganese. duce 2-ethyl-3-naphthylcyclopentadienyl manganese tri The bis(cyclopentadienyl-type) manganese compound carbonyl. need not be separated from the reaction mixture in which Example VII 70 it is prepared. The metal carbonylic compound may be added directly to such a mixture as illustrated in Example Bis(methylcyclopentadienyl)manganese and iron car II. A diluent or liquid medium is not necessary for the bonyl are vaporized in separate containers and the vapors reaction between the cyclomatic manganese compound combined and passed into ally tolyl ether in a reaction and the metal carbonylic compound as has been illustrated vessel maintained at a temperature of substantially 100 75 in Example I. However, when a medium is employed, it 2,870,180 1. 12 can consist of a hydrocarbon, an ether, or an inert gas, tion of the cyclopentadienyl group attached to the man non-limiting examples of which are n-butyl ether, dodecyl ganese, compounds having "tailormade' characteristics ether, anisole, dioxane, tetrahydrofuran, ethylene glycol can be obtained. For example, cyclopentadienyl man dimethyl ether, ethylene glycol diethyl ether, methyl ganese tricarbonyl is a solid melting at 77° C., whereas phenyl ether, diethyl ether, ally tolyl ether, benzene, cy methylcyclopentadienyl manganese tricarbonyl is a liquid clohexane, toluene, Xylene, nitrogen, argon, helium, meth at ordinary temperatures, such as 23° C. In like manner, ane, ethane, etc. A mixture of two or more of any of the nature of the cyclopentadienyl group on the man the above type of solvents or diluents can be employed ganese affects the solubility of the compound in various as is the case when nitrogen is used as a carrier gas for hydrocarbon and other solvents. Thus, it is seen that transporting the vapors of the reactants into a reaction O our process can be used to make cyclomatic manganese vessel containing an ether as a reaction medium. When tricarbonyl compounds which are better adapted for hydrocarbon and ether solvents or diluents are employed, Specific uses by choosing the right cyclopentadienyl group they may have up to 20 or more carbon atoms. An ex as a substituent. ample is dodecyl ether having 24 carbon atoms. Having fully described the process of this invention, The process of our invention can be carried out within the need therefor, and the best method for carrying out the range of from below 0° C. to about 250° C. A pre the process, we do not intend that our invention be lim ferred range is from 20° C. to about 200° C. as it is ited except within the spirit and scope of the appended found that the reaction proceeds at a satisfactory rate in claims. this range. The requirement in all cases is that the tem We claim: perature be kept below the decomposition temperature 20 1. A process for the preparation of hydrocarbon cyclo of the reactants. When Fe(CO)5 is employed, for ex matic manganese tricarbonyl compounds having the gen ample, the temperature should be not higher than 130 C. eral formula The time required to obtain a particular yield of pro RMn(CO) duct, that is, the residence time of the reactants in the reaction vessel, varies depending on the particular mode 25 wherein R is a cyclomatic hydrocarbon radical having in which our process is carried out. For example, when from 5 to 17 carbon atoms which embodies a group of 5 the reactants are reacted in the vapor phase in a thermal carbons having the general configuration found in cyclo reactor, the residence time may be of an order of a few pentadiene, Said compounds being further character seconds. On the other hand, when the reaction is con ized in that the cyclomatic hydrocarbon radical is bonded ducted in a liquid phase, the contact time may be a mat 30 to the manganese by carbon-to-manganese bonds through ter of 2 minutes to 20 hours, depending on the tempera the carbons comprising the cyclopentadienyl-group con ture used and the reactivity of the reagents employed. figuration, said process comprising reacting a manganese One advantage of our process is that the reaction can compound having the general formula be conducted at atmospheric pressure especially when the RMR process is carried out in the liquid or condensed phase. 35 However, the process is operable at pressures below at wherein R and R' have the composition defined for R mospheric as well as at elevated pressures which may be above with a metal carbonylic compound having the gen as high as 20,000 atmospheres. eral formula Our process has a number of advantages in addition M(CO).X.R.H. to the benefit of low pressure operability. One of the 40 wherein M is a metal having an atomic number of from added advantages is the higher yield of product obtained 23 to 79, selected from groups I-B, V-B, VI-B, VII-B, due to initimate contact of reactants especially when and VIII, X is a halogen having an atomic number of conducted in the liquid phase. Thus, cyclopentadienyl from 9 to 53, R is as defined above, a is a number from type manganese tricarbonyl compounds are obtained 1 to 4 inclusive, b is a number from 1 to 11 inclusive, without having to resort to special apparatus for contact c has a numerical value of from 0 to 3 inclusive, d has ing carbon monoxide gas under elevated pressures with a numerical value of from 0 to 1 inclusive, f has a numer cyclopentadienyl-type manganese compounds. Our proc ical value of from 0 to 2 inclusive, and the sum ess also produces valuable by-products. To illustrate, a--b-c-d--if has a value of from 3 to 15 inclusive said when cyclopentadienyl-type manganese compounds are re process being conducted at temperature below the decom acted with group VIII-metal carbonyl compounds, the 50 position temperature of said metal carbonylic compound. product contains, in addition to the cyclopentadienyl-type 2. The process of preparing methylcyclopentadienyl manganese tricarbonyl compounds, cyclopentadienyl-type manganese tricarbonyl, comprising reacting bis(methyl group VIII metal compounds and cyclopentadienyl-type cyclopentadienyl)manganese with iron pentacarbonyl at group VIII metal carbonyl compounds. For example, a temperature of substantially 80° C. when iron pentacarbonyl is reacted with cyclopentadienyl 55 3. A process for the preparation of methylcyclopenta manganese compounds, the by-products consist of dicyclo dienyl manganese tricarbonyl comprising reacting man pentadienyl diron tetracarbonyl and bis(cyclopentadi ganous chloride with methylcyclopentadienyl sodium and enyl)iron which can be separated from the reaction prod Subsequently reacting the reaction mixture thus obtained uct by fractional distillation, Sublimation, etc. One of with iron pentacarbonyl at a temperature of substantially the products when cobalt carbonyl, such as Co(CO)42 60 80° C. and separating the methylcyclopentadienyl man is reacted with a cyclopentadienyl-type manganese com ganese tricarbonyl, di(methylcyclopentadienyl)iron and pound, such as bis(methylcyclopentadienyl)manganese, is di(methylcyclopentadienyl) diiron tetracarbonyl products methylcyclopentadienyl cobalt dicarbonyl. In like man therefrom. ner, cyclopentadienyl derivatives are formed of other 4. A process for the preparation of hydrocarbon cyclo metal carbonylic compounds when the latter are reacted matic manganese tricarbonyl compounds having the gen with manganese cyclopentadienyl-type compounds accord eral formula ing to the process of our invention. These cyclopentadienyl-type manganese tricarbonyl RMn(CO) compounds prepared by the process of our invention are wherein R is a cyclomatic hydrocarbon radical having found to be exceptionally good agents for improving the 70 from 5 to 17 carbon atoms which embodies a group of 5 antiknock quality of hydrocarbon fuels used in Spark igni carbons having the general configuration found in cyclo tion engines. They can also be used as chemical inter pentadiene, said compounds being further characterized mediates in the synthesis of other manganese compounds. in that the cyclomatic hydrocarbon radical is bonded to A particular advantage of the manganese compounds the manganese by carbon-to-manganese bonds through produced by our process is the fact that by proper selec 5 the carbons comprising the cyclopentadienyl-group con 2,870,180 13 14 figuration, said process comprising reacting a manganese process being conducted at a temperature between about compound having the general formula 0 to about 250' C, RMR' References Cited in the file of this patent abovewherein with R anda metalR' have carbonylic the composition compound defined having for the R 5 UNITED STATES PATENTS general formula 2,791,597 Anzilotti et al. ------May 7, 1957 M(CO)5XRHy 2,818,416 Brown et al. -----ww to uka Dec. 31, 1957 wherein M is a metal having an atomic number of from O 2,818,417 Brown et al. ------Dec. 31, 1957 23 to 79, selected from groups I-B, V-B, VI-B, VII-B, and VIII, X is a halogen having an atomic number of OTHER REFERENCES from 9 to 53, R is as defined above, a is a number from Fischer et al.: "Zeit. ftir Naturfor.' Band 7B, Heft 7, 1 to 4 inclusive, b is a number from 1 to 11 inclusive, July 1952, pp. 377-79. c has a numerical value of from 0 to 3 inclusive, d has a Fischer et al.: "Zeit. ftir Naturforsch" vol. 9B, page numerical value of from 0 to 1 inclusive, f has a nu- 15 618 (1954). merical value of from 0 to 2 inclusive, and the sum Mellor: “Mod. Inorg. Chem.” pp. 867-877, Longmans a-b-c-d--if has a value of from 3 to 15 inclusive, said Green & Co., N.Y.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,870,180 January 20, 1959 John Kozikowski et al. It is hereby certified that error appears, in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. Column 2, line 12, for “ (CO)” read-M(CO)-; column 5, lines 25 to 30, the formula should appear as shown below instead of as in the patent: R4 R Rs
R Rs R R (II) column.6, line 26, for “hydrocarbon read hydrocarbo -; column , line 12, for “WB-I' read - VI-B-; line 30, for "Os (CO)' read-Os (CO)-; column 9, line 27, for Re(CO)Cl” read -Re(CO)C1-; same line 27, for “Fe(CO),” read “hydrocarbon”-Fe(CO)-; columnread -hydrocarbons-. 10, line 6, for “for” read -form-; column 12, line 9, for Signed and sealed this 4th day of August 1959.
sEAL
Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attesting Officer. Commissioner of Patents.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,870,180 January 20, 1959 John Kozikowski et al. It is hereby certified that error appears in the printed specification of the above numberedas corrected patent below. requiring correction and that the said Letters Patent should read formulaColumn should 2, lineappear 12, asfor shown “(CO)' below read-Ma instead of (CO)-; as in the column patent: 5, lines 25 to 30, the R R Rs
R Re R R (II) column 6, line 26, for “hydrocarbon read hydrocarbo ; column 7, line 12, for “WB-I' read-VT-B-; line 30, for "Os (CO), read-Os (CO)-; column 9, line 27, for Re(CO)3Cl’ read -Re(CO)5C1-; same line 27, for “Fe(CO),” read “hydrocarbon”-Fe(CO)-; columnread -hydrocarbons 10, line 6, for “for” read -form-; column 12, line 9, for Signed and sealed this 4th day of August 1959.
SEAL
Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attesting Officer. Commissioner of Patents.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,870,180 January 20, 1959 John Kozikowski et al. It is hereby certified that error appears in the printed specification of the above asnumbered corrected patent below. requiring correction and that the said Letters Patent should read formulaColumn should 2, lineappear 12, asfor shown “ (CO)' below read instead -M(CO)-; of as in the column patent: 5, lines 25 to 30, the R4
R R (II) column 6, line 26, for “hydrocarbon read -hydrocarbo-; column 7, line 12, for “WB-I' read-VT-B-; line 30, for "Os (CO),” read-Osa(CO)-; column 9, line 27, for "Re(CO)3Cl” read -Re(CO)5C1-; same line 27, for “Fe(CO),” read “hydrocarbon”Fe(CO)-; columnread -hydrocarbons-. 10, line 6, for “for” read -form-; column 12, line 9, for Signed and sealed this 4th day of August 1959.
sEAL
Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attesting Officer. Commissioner of Patents.