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' rite 3,659,449 Patented Dec. 18, 1962

2 both unleaded and conventional leaded gasolines made 3,tl69,44~9 from a Wide variety of base stocks. Of the compounds BlMETALLIC CYCLQI’ENTADIENYL CARBONYL CUMI’QUNDS AND E’REPARATION THEREGF encompassed by this invention, those containing both lead Richard I). Gorsieh, Baton Rouge, La., assignor to Ethyl and iron or both lead and nickel are preferred as anti @ct‘poration, New York, N.Y., a corporation of Dela detonants because of the powerful antiknock effects pro ware duced thereby. The most outstanding antiknocks are the No Drawing. Filed .luly 26, 1961, Scr. No. 126,865 dialkyllead bis(cyclopentadienyliron dicarbonyls), espe 29 @laims. {$1. see-429.7) cially those compounds in which the alkyl groups are methyl or ethyl, or a combination of these. This invention relates to, and has as its principal ob 10 Thus, gasoline fuel compositions containing the novel jects, the provision of novel organobimetallic compounds compounds of this invention in amounts suf?cient to in wherein one metal is selected from group IV~A and the crease the antiknock ratings thereof and, in particular, other from group VIII of the periodic system, and the those containing a dialkyllead bis(cyclopentadienyliron provision of novel methods for the preparation of such dicarbonyl) are highly effective fuels for internal combus compounds, the novel compounds being of particular use 15 tion engines, the use of which is characterized by smooth as autiknock agents in motor fuels and for other purposes. ness of engine operation. The compositions of this invention are organobimetallic That the compounds of this invention are highly ver compounds of the general formula satile is shown by the fact that their use as antiknock addi tives not only involves clear-—i.e., unleaded-fuels, but 20 includes leaded fuels as well, that is, fuels containing a In this formula R is a cyclopentadienyl or alkyl- or previously known alkyllead antiknock compound such as aeyl-substituted cyclopentadienyl group containing from 5 tetraethyllead or containing a mixture of such alkyllead to about 18 , or is an idenyl or fluoroenyl compounds. Thus, a liquid fuel for Otto group; R’ is a hydrocarbon group, preferably an alkyl, cycle engines containing antiknock-increasing amounts of aryl, cycloalkyl, aralkyl, alkaryl, or alkenyl radical con ' both a tetraalkyllead compound and a lead-containing taining from 1 to about 18 carbon atoms; M4 is an element compound of this invention is superior in antiknock edec of group IV-A of the periodic system having an atomic tiveness to the same fuel containing a like amount of either number from 32 to 82, inclusive, i.e., germanium, tin or of said compounds in the absence of the other. Best results lead; M8 is an element of group VIII of the periodic system occur when the concentration of the tetraalkyllead com having an atomic number from 26 to 78, inclusive, i.e., 30 pound is equivalent to from about 0.5 to 6.0 grams of lead iron, cobalt, nickel, ruthenium, rhodium, palladium, per gallon and the concentration of the carbonyl com osmium, iridium, or platinum; X is a ; a is 1 when pound is equivalent to from about 0.01 to 4.0 grams of M8 is cobalt, nickel, rhodium, palladium, iridium or lead per gallon. platinum, and is 2 when M8 is iron, ruthenium, or osmium; The preferred antiknock fuels of the invention (because b is an integer from 1 to 3, inclusive; c is an integer from of their economy and availability) are leaded or unleaded 0 to 3, inclusive; and the sum of b and c is less than 5. gasolines containing a compound of the formula The compositions of this invention are, in general, liquid or solid compounds, the solids melting at low or moderate temperatures. They are stable at ordinary temperatures or a compound of the formula RFe(CO)2M4R’3 wherein and can readily be prepared and stored without special 40 M4 is tin or lead; R is a cyclopentadienyl or lower alkyl precautions for future use. The lead compounds melt, in or acyl-substituted cyclopentadienyl group, e.g., methyl general, at lower temperatures than the corresponding tin cyclopentadienyl or acetylcyclopentadienyl, or is an compounds and the melting points tend to increase with indenyl or lluoroenyl group; and R’ is a lower alkyl group, the number and molecular weights of the organic sub e.g., methyl, ethyl, pentyl, etc., or is an aryl group having stituents designated above as R’ as well as with the number up to 8 carbon atoms, e.g., phenyl, tolyl, xylyl, etc. and atomic weights of the halogen substituents. In addition to their effectiveness as antiknock agents for These compounds vary in color from white through hydrocarbon fuels, the compounds of this invention are yellow to orange. The depth of color tends to increase excellent lubricant additives. In this application, as well with the atomic weight of the group IV—A metal, with the as in fuels, they exhibit unusual versatility. Thus, when number and atomic weight of the halogen atoms and with 50 dissolved in lubricants, they effectively improve the lubri the number of group VIII groups in the cating properties thereof, greatly reduce engine wear, . virtually eliminate frictional damage, and/ or bring about The compounds of this invention in general are soluble improvements in stability. Their versatility is further in organic such as aliphatic and aromatic hydro attested to by the wide variety of natural and synthetic , e.g., n-hexane, petroleum . and ; lubricant bases in which they produce the above effects. in alcohols such as and hexanol; in halohydro» For example, they are highly eifective for the above and carbons such as methylene dichloride and carbon tetra other purposes in such lubricating and industrial oils as ; in ether such as , methyl ethyl crank-case lubricating oils, transformer oils, turbine oils, ether, and tetrahydrofuran; and in mixtures of the fore transmission ?uids, cutting oils, glass annealing oils, gear going. 65) oils, mineral white oils, oils thickened with soaps and Of the metals represented by M4 in the above formula, inorganic thickening agents, hydraulic ?uids and, in gen lead is preferred for several reasons. It is readily sepa eral, engine and industrial oils which are derived from rated from its ores, is available in large quantity, and is crude petroleum or produced synthetically. considerably cheaper than the other metals. Consequently, Typical of these synthetic lubricants are the polybutene the lead compounds of the invention are more adapted for 65 oils, the ester oils, the silicone oils, phosphates, phospho preparation on a larger scale, thereby taking advantage of nates, and the like. The ester oils include such com~ the economies normally associated with large-scale opera pounds as di-Z-ethylhexyl sebacate, di-sec-amyl sebacate, tions. di-Z-ethylhexyl azelate, di-3-methylbutyl adipate, di-Z The novel compounds of this invention are of value in ethylhexyl adipate, diisooctyl adipate, di-Z-ethylhexyl the chemical and allied arts. For example, the lead com phthalate, dibutoxyethyl phthalate, pentaerythritol tetra pounds are potent antiknock agents, and in this utility they caprcate, triethylene glycol di-Z-ethylhexanoate, and poly are versatile agents in that they are highly effective in ethylene glycol di-Z-ethylhexanoate. Examples of the'sili o a 4: cone oils are the dimethyl, divinyl, diphenyl, methylvinyl, lead; X is a halogen, i.e., ?uorine, , , or methylphenyl, diethyl, dibutyl, di-p-bromophenyl, di-p ; b is 1, 2 or 3; c is O, 1, 2 or 3; and the sum of chlorophenyl, di-p-?uorophenyl, di - m - tri?uoromethyl b and c does not exceed 4. In this process, one or more phenyl, di-p-phenoxyphenyl, di-m-chlorophenyl, di-3,4 of the halogen atoms of the organometal halide reactant dichlorophenyl, di-3-chloro-4-bromophenyl, di-p-meth re replaced by the cyclopentadienyl group VIII metal oxyphenyl, and di-p-cyanophenyl siloxanes, i.e., silicone mono- or dicarbonyl group of the carbonyl reactant, and derivatives. the displaced halogen combines with the alkali metal of Among the most effective compounds of this invention the carbonyl reactant to form an inorganic salt. In the as lubricant additives are those containing nickel bonded carbonyl reactant, the preferred alkali metal is sodium or to lead and, particularly, to tin. Thus, these are the 10 potassium because of the abundance and ready availabil preferred lubricant additives for use in accordance with ity of these metals and, of these, sodium is particularly this invention. preferred because of its economy. Similarly, the pre Accordingly, hydrocarbon lubricant compositions con- ' ferred group VIII metals, because of their abundance and taining, in amounts su?icient to improve the lubricating availability, are iron, cobalt and nickel, and of these iron properties thereof, the novel compounds of this invention is particularly preferred because of its economy. With wherein M8 is nickel and M4 is lead, or tin, and, in par reference to ‘the organometal halide reactant, the pre ticular, those containing a cyclopentadienylnickel dicar ferred group IV-A metals are tin and lead because of bonyl trialkyltin, are effective lubricants for internal com their abundance, availability and economy and, of these, bustion engines and for other applications. lead is particularly preferred when the product is to be An excellent feature of these lubricant additives is that 20 used for antiknock applications, because of the known they can be used not only in a wide variety of oils but also high antiknock e?icacy of this element, and tin is par in combination with other additives without in any way ticularly preferred for similar reasons when the ?nal prod impairing their effectiveness or that of the other addi uct is to be used in antiwear applications. tives. Such other additives include, for example, anti The nature of the product obtained in the metathesis oxidants, metal deactivators, detergent-dispersants, pour 25 process obviously depends upon the nature of the reactant point depressants, index improvers, antifoam components which unite to form the ?nal product, but agents, corrosion inhibitors, oiliness or ?lm strength also, less obviously, on the number of halogen atoms in agents, dyes, and the like. the organometal halide reactant and on the relative pro The preferred lubricants of the invention are the cheap portions of the two reactants used. Speci?cally, if the and readily available liquid hydrocarbon crankcase lu 30 reactants are combined in such proportions that the alkali bricating oils containing from about 0.05 to about 5.0 metal is equivalent to the halogen present, the product weight percent of nickel as a compound of the formula will contain no halogen but will have one cyclopenta RNi(C'O)M4R’3 wherein M4 is tin or lead, R is a cyclo dienyl group VIII metal carbonyl radical for each halogen pentadienyl or lower alkyl- or acylcyclopentadienyl originally present in the organometal halide. If an group, e.g., methylcyclopentadienyl or acetylcyclopenta excess of the organometal halide reactant is used, the dienyl, or ‘is an indenyl or ?uorenyl group, and R’ is a product will contain halogen in an amount proportional lower alkyl group, e.g., methyl, ethyl, pentyl, etc., or is to that excess. In the former case, a typical product is an aryl group having up to about 8 carbon atoms, e.g., cyclopentadienyl iron dicarbonyl triphenyltin, or bis(cy phenyl, tolyl, xylyl, etc. clopentadienyliron dicarbonyl)dimethyltin, in the latter, In addition to the foregoing uses, the compounds of this 40 methylcyclopentadienylcobalt carbonyl ethyltin chloride. invention ?nd application as plasticizers and stabilizers for Evidently, if the reactants are used in non-stoichiometric vinyl and other synthetic resins such as polyvinyl chloride. proportions, or if the reaction does not reach completion, There are two general methods of preparing the com a mixture of products will be obtained. pounds of this invention, namely (1) a metathesis proc The metathesis reaction of this invention is normally ess wherein a cyclopentadienyl group VIII metal car 45 carried out in an inert organic such as a hydro bonyl derivative of an alkali metal is reacted with an carbon or an ether. Ethers are generally preferred be alkyl halide derivative of a group IV-A metal, and (2) cause of their solvent power for the reactants, and tetra the hydrohalogenation process wherein a cyclopenta hydrofuran is particularly preferred because of the ready dienyl group VH1 metal carbonyl derivative of a group of the reactants therein, its and conse- IV-A metal alkyl or of an alkyl group IV-A metal halide 50 quent ease of separation from the reaction products, and is reacted with hydrogen halide. Consequently, these the ease with which the solvent may be made and kept two processes constitute embodiments of this invention. anhydrous. METATHESlS PROCESS The metathesis reaction of this invention proceeds smoothly and rapidly at room temperature or at slightly In the metathesis process, the cyclopentadienyl group elevated temperatures, reaching completion for the reac VIII metal carbonyl alkali metal reactant is represented by tion of lower alkyl derivatives of the group IV-A metal the general formula RM8(CO),,M1d, wherein R is a cyclo halides with carbonyl reactants containing an unsub~ pentadienyl, alkylcyclopentadienyl or acylcyclopenta stituted cyclopentadienyl radical in 1 to 3 hours at 20 to dienyl radical, containing from 5 to about 18 carbon 60° C. Somewhat longer reaction times are desirable for atoms, or is an indenyl or fluorenyl radical; M3 is an ele 60 the higher alkyl and substituted cyclopentadienyl deriva ment of group VIII of the peroidic system having an tives. The reaction temperature can vary from room tem atomic number from 26 to 78, inclusive, i.e., iron, cobalt, perature or below to the normal re?ux temperature of nickel, ruthenium, rhodium, palladium, osmium, iridium the solvent or even higher if pressure is employed. How or platinum; M1 is an alkali metal, i.e., lithium, sodium, ever, elevated temperatures should be used with care potassium, rubidium, or cesium; a is 1 when M8 is cobalt, since prolonged heating at re?ux may cause some de nickel, rhodium, palladium, iridium or platinum, and is composition of the reaction product. The pressure em 2 when M8 is iron, ruthenium or osmium; and d is 1 when ployed may range from 10 millimeters of mercury or M8 is iron, nickel, ruthenium, palladium, osmium or plat less to 100 atmospheres or more but, in general, normal inum, and is 2 when M8 is cobalt, rhodium or iridium. In atmospheric pressure is wholly satisfactory and is pre this process, the organometal halide reactant is represented 70 ferred. by the general formula R'4nb_cM4Xb+c, wherein R’ is an alkyl, aryl, cycloalkyl, aralkyl, alka'ryl, or alkenyl radical HYDROHALOGENATION PROCESS containing up to about 18 carbon atoms; M4 is an element In the hydrohalogenation process, as indicated above, of group lV-A of the periodic system having an atomic reaction occurs between a hydrogen halide and a cryclo number from 32 to 82, inclusive, i.e., germanium, tin or 75 pentadienyl group VIII metal carbonyl derivative of an £2,069,449 organo group IV-A metal halide (obtained by the met by adding 10.6 parts (0.03 mole) of cyclopentadienyliron athetic reaction discussed above). In this reaction the dicarbonyl dimer to a mixture of about 250 parts of alkyl groups attached to the group IV-A metal of the tetrahydrofuran and sodium amalgam (3 parts of sodium carbonyl reactant are replaced wholly or in part by the and 300 parts of mercury). The brown mixture was halogen component of the hydrogen halide reactant. stirred under as room temperature overnight. This reaction is normally carried out by combining the Subsequently, the mercury was drained off and to the re reactants in the presence of a halohydrocarbon solvent. sulting brown mixture was added 20 parts of triphenyltin The nature of the product of the hydrohalogenation re chloride. The mixture was stirred at room temperature action is closely related to the ratio of the amounts of for 2 hours and then the solvent was evaporated under reactants used. Thus, the use of an excess of the hydro reduced pressure (water aspirator) at 55° C. The prod gen halide reactant favors the formation of a product uct was extracted from the residue by means of methylene containing halogen but no alkyl groups directly attached chloride and was then recrystallized from n-hexane to to the group IV~A metal, whereas the use of an excess give 10.65 parts of cyclopentadienyliron dicarbonyl tri of the carbonyl reactant favors the formation of a prod phenyltin, melting at 138 to 140° C. The product, re uct containing both halogen and alkyl groups directly ‘ crystallized from ethanol, melted at 139 to 141° C. attached to the group lV-A metal. The reaction product is normally a mixture of compounds containing varying Example 11 proportions of halogen and alkyl groups directly at~ A solution of cyclopentadienyliron dicarbonyl sodium tached to the group IV-A metal, which mixture can was prepared by adding 9 parts (0.03 mole) of cyclopen readily be separated by solvent extraction, fractionation, tadienyliron dicarbonyl dimer in small portions to a mix or other appropriate means. ture of 200 parts of tetrahydrofuran and sodium amal The hydrohalogenation reaction of this invention is nor gam (3.5 parts of sodium and 350 parts of mercury). mally carried out in an inert organic solvent. Halohydro The mixture ‘was stirred at room temperature for 17 carbons are generally preferred because of their inertness hours, after which the mercury was drawn. off. To the to and their solvent power for the reactants, and the chlo stirred mixture was added a solution of 7.2 parts (0.03 romethanes are particularly preferred because of the ready mole) of dimethyltin dichloride in 30 parts of tetrahydro solubility of the reactants therein, their volatility and furan during a 1-hour period. On completion of the ad consequent ease of separation from the reaction products, dition, the reddish-brown mixture had become distinctly and the ease with which the solvent may be made and yellow. The solvent was evaporated in vacuo (water kept anhydrous. aspirator at 55°). The residue was briefly suspended The hydrohalogenation reaction of this invention in water, then ?ltered and dried at 0.2 millimeter (room proceeds smoothly and rapidly at room temperature or at temperature). The solid was repeatedly extracted with slightly elevated temperatures, reaching completion with hot n-hexane and the combined extracts were concen carbonyl reactants containing unsubstituted cyclopen trated until crystals began to settle out. The mixture tadienyl radicals and alkyl groups of low molecular was allowed to cool to room temperature and was fur weight in 10 minutes to a half hour, at 15 to 35° C. ther cooled by an ice bath. The brown crystals formed Somewhat longer reaction times are desirable for the were ?ltered off and dried in vacuo to give 10.92 parts of higher alkyl and substituted cyclopentadienyl derivatives. product melting at 105 to 107°. Workup of the filtrate The reaction temperature can vary from room tempera gave an additional 0.75 part of product melting at 98 to ture or below to the normal reiiux temperature of the V to 100°. The total yield of bis(cyclopentadienyliron di solvent, or even higher if pressure is employed. How carbonyl) dimethyltin was 11.7 parts or 78 percent. ever, elevated temperatures are normally unnecessary Analysis.-Calculated for C16l~I1GO4Fe2Sm C, 38.23; since the reaction proceeds with adequate speed at room H, 3.29. Found: C, 38.50, 38.50; H, 3.33, 3.34 temperature and should be used with care since pro Example 111 longed heating at reflux may cause some decomposition of the reaction product. The pressure employed may Two parts (0.0038 mole) of cyclopentadienyliron di range from 10 millimeters of mercury or less to 100 at carbonyl triphenyltin were dissolved in about 90 parts of mospheres or more, but in general, normal atmospheric methylene dichloride. Anhydrous was pressure is wholly satisfactory and is preferred. passed through the solution for 10 minutes at room tem perature, after which time the solvent was evaporated. PREPARATION OF REACTANTS The product, 1.43 parts of cyclopentadienyliron dicar The cyclopentadienyl group VIII metal dicarbonyl bonyl tin trichloride, was recrystallized from a mixture alkali metal reactants required for the metathesis reac» of methylene dichloride and carbon tetrachloride to give tion described above are prepared by treating a cyclopen 1.3 parts of reddish~brown needles melting at 150° C. with tadienyl group VIII metal mono- or dicarbonyl with an decomposition. alkali metal. Thus, for example, cyclopentadienyliron Analysis.—-Calculated for CqH5Cl3O2FeSn: C, 20.91; dicarbonyl sodium may be obtained as follows: H, 1.25; Sn, 29.5. Found: C, 21.02; H, 1.30; Sn, 30.2. Cyclopentadienyliron dicarbonyl sodium is prepared by adding 10.6 parts (0.03 mole) of cyclopentadienyliron Example I V dicarbonyl dimer to a mixture of about 250 parts of When 10.0 parts of cyclopentadienyliron dicarbonyl so tetrahydrofuran and sodium amalgam (3 parts of so 60 dium are reacted with 8.60 parts of diphenyltin dichloride dium and 300 parts of mercury). The mixture is stirred in 930 parts of tetrahydrofuran at 25' to 31° C. for a under nitrogen at room temperature for 17 hours after period of 1% hours and the resultant orange crystals are which the mercury is drained off and the resulting brown recrystallized from ethanol, bis(cyclopentadienyliron di mixture is used without further treatment for the meth carbonyl)diphenyltin is obtained. athesis reaction. Example V Modi?cations in the above procedure to make the other organo group VIII metal carbonyls of alkali metals used Cyclopentadienyliron dicarbonyl sodium and dimethyl in the process of this invention will now be apparent to lead dichloride in the proportion of 10.0v parts of the those skilled in the art. former to 7.7 parts of the latter are dissolved in 890 parts The invention will be more fully understood by refer~ 70 of tetrahydrofuran and are reacted at room temperature ence to the following set of illustrative examples in which for 1 hour. The product, bis(cyclopentadienyliron dicar all parts and percentages are by weight. bonyl)dimethyllead, may be puri?ed by recrystallization from n-hexane. Example I Example VI Cyclopentadienyliron dicarbonyl sodium was prepared Cyclopentadienyliron dicarbonyl lithium (4.60 parts) 3,069,449 8 and dimethylgermanium di?uoride (3.52 parts) are dis to 50° C. and maintained in this temperature range for solved in 406 parts of benzene. The mixture is stirred for 2 hours. Dodecylcyclopentadienyliron dicarbonyl diben 1 hour at 25 to 32° C. The product obtained is cyclo zylgermanium chloride is obtained. pentadienyliron dicarbonyl dimethylgermanium ?uoride. Example XVI Example VII Tetrahydroturan solutions of 11.37 parts of cetylcyclo A mixture of 5.30 parts of methylcyclopentadienylco pentadienylcobalt carbonyl dipotassium and 8.26 parts of balt carbonyl disodium and 6.35 parts of ethyltin tri phenethyltin trichloride are mixed and the mixture is dis chloride is dissolved in 580 parts of toluene and allowed solved in 980 parts of tetrahydrofuran. The product is to stand for 2 hours at 24 to 30° C. With occasional stir-' 10 cetylcyclopentadienylcobalt carbonyl phenethyltin chlo ring. The compound produced is methylcyclopentadienyl ride. cobalt carbonyl ethyltin chloride. Example XVII Example VIII A mixture of 18.65 parts of acetylcyclopentadienyl nickel carbonyl o-tolyllead diiodide, 3.20 parts of hydrogen Ethylcyclopentadienylnickel carbonyl dimethyllead bro iodide and 1100 parts of ethylene dichloride is stirred at mide (12.43 parts) is dissolved in 620 parts of ethylene 26 to 31° C. for 50 minutes. Acetylcyclopentadienyl dibromide and is passed into the solu nickel carbonyl lead triiodide is obtained. tion for 20 minutes at 26 to 31° C. The product, ethyl cyclopentadienylnickel carbonyl lead tribromide, is puri Example XVIII ?ed by recrystallization from a mixture of methylene di 20 A mixture of 42.0 parts of octadecylcyclopentadienyl chloride and methylene dibromide. ruthenium dicarbonyl rubidium, 5.9 parts of 2,4-xylyl Example IX germanium tri?uoride and 2400 parts of benzene is heated to 50 to 60° C. for a period of 31/2 hours. The product To 22.76 parts of methylethylcyclopentadienylruthen is tris(octadecylcyclopentadienylruthenium dicarbonyl) ium dicarbonyl potassium, 14.16 parts of octylgermanium 2,4-xylylgermanium. triiodide is added and the mixture is dissolved in 850 parts Example XIX of o-xylene. The mixture is allowed to stand with oc casional stirring for 2 hours at 42 to 50° C. Octyl 12.8 parts of indenylrhodium carbonyl dicesium are add germanium tris(methylethylcyclopentadienylruthenium di ed to a mixture of 7.3- parts of cyclopentadienyltin tri carbonyl) is obtained. chloride With 1000 parts of toluene and the mixture is Example X stirred at 40° C. for 3 hours. The product is indenyl Dimethylcyclopentadienylrhodium carbonyl dirubidiurn, rhodium carbonyl cyclopentadienyltin chloride. dodecyltin tri?uoride and petroleum naphtha are com Example XX bined in the ratio 9.88:8.631925. The mixture is warmed When 15.3 parts of ?uorenylpalladiurn carbonyl bis to 40 to 46° C. for a period of 1% hours. The product, . (methylcyclopentadienyl)germanium bromide are dis puri?ed by recrystallization from methylene dichloride, is solved in 900 parts of and hydrogen bromide dimethylcyclopentadienylrhodium carbonyl dodecyltin is passed into the solution for a half hour at room tem ?uoride. I perature, ?uorenylpalladium carbonyl methylcyclopenta Example XI dienylgermanium dibromide is obtained. 40 Diethylcyclopentadienylpalladium carbonyl tricyclo Example XXI hexyllead (18.51 parts) is dissolved in carbon tetrachlo ride (1000 parts) and dry hydrogen chloride is passed into 'Cyclopentadienylosmium dicarbonyl lithium and tri the solution for 1/2 hour at 23 to 31° C. Diethylcyclo vmylgermanium iodide in the proportion of 8.0 parts of pentadienylpalladium carbonyl cyclohexyllead dichloride the former to 7.0 parts of the latter are dissolved in 750 is obtained in good yield. — parts of o-xylene and are reacted at room temperature for a period of 2 hours. The product is cyclopenta Example XII dlenylosmlum dicarbonyl trivinylgermanium. When 12.51 parts of butylcyclopentadienylosmium di Example XXII carbonyl cesium and 13.20 parts of tris(acetylcyclohexyl) germanium bromide are mixed with 1300 parts of benzene 50 Methylcyclopentadienyliridium carbonyl disodium (8.6 and the mixture is reacted for 3 hours at 26 to 32° C., parts) and diallyltin di?uoride (6.0 parts) ‘are dissolved 'butylcyclopentadienylosmium dicarbonyl tris(acetylcyclo in 730 parts of petroleum naphtha. The mixture is stirred hexyl)germanium is obtained. for 1 hour at 39 to 45° C. The product is methylcyclo— Example XIII pentadienyliridium carbonyl diallyltin. To 10.29 parts of octylcyclopentadienyliridium carbonyl Example XXIII dilithium, 18.82 parts of dioctadecyltin diiodide are added 22.0 parts of ethylcyclopentadienylplatinurn carbonyl and the mixture is dissolved in 1460 parts of the diethyl trimesityllead are dissolved in 1200 parts of ethylene di ether of diethylene glycol. The resulting mixture is chloride and hydrogen. chloride is passed into the solution warmed gently for three hours. The product is octyl 00 for a period of a half hour. The product is ethylcyclo cyclopentadienyliridium carbonyl dioctadecyltin. pentadienylplatinurn carbonyl lead trichloride. Example XIV Example XXIV 24.48 parts of octadecylcyclopentadienylplatinum car A mixture of 6.5 parts of methylethylcyclopentadienyl bonyl triphenyllead are dissolved in 1300 parts of methyl iron dicarbonyl potassium and 12.2 parts of di-a-naphthyl ene dichloride and the mixture is treated With a methylene germanium dibromide is dissolved in 930 parts of diethyl dichloride solution of 0.50 part or" hydrogen ?uoride. Re ether and heated under re?ux for 2 hours. The product action for 1/2 hour at room temperature results in the is methylethylcyclopentadienyliron dicarbonyl di-a-naph formation of octadecylcyclopentadienylplatinum carbonyl thylgermanium bromide. diphenyllead ?uoride. Example XV Example XXV 9.21 parts of dodecylcyclopentadienyliron dicarbonyl To 8.8 parts of dimethylcyclopentadienylcobalt car sodium are reacted with a mixture of 8.14 parts of di bonyl dirubidium, 15.4 parts of indenyltin triiodide are benzylgermanium dichloride and 870 parts of the dibutyl added and the mixture is dissolved in 1200 parts of the ether of diethylene glycol. The mixture is heated to 43 diethyl ether of diethylene glycol. The mixture is stirred 3,069,449 9 10 for 2 hours at 40° C. Dimethylcyclopentadienylcobalt crenyliron dicarbonyl)butylgermanium, methylcyclopen carbonyl indenyltin iodide is obtained in good yield. tadienylcobalt carbonyl tin diiodide, bis(diethylcyclo Example XX V1 pentadienylnickel carbonyUmethyllead bromide, cyclo pentadienylruthenium dicar'oonyl diphenylgermaniurn Diethylcyclopentadienylnickel carbonyl di?uorenyltin chloride, indenylpalladium carbonyl o-tolyltin difluoride, ?uoride, hydrogen ?uoride and 1,1,2-trichloro-1,2,2-tri iiuorenylrhodium carbonyl dioctyllead, cyclopentadienyl ?uoroethane are combined in the ratio 21.3:1: 1100. The iridium carbonyl dicetyllead and methylcyclopentadienyl mixture is reacted at room temperature for a period of osmium dicarbonyl methyldipropylgermanium. Of the 20 minutes. The product is diethylcyclopentadienylnickel carbonyl tin tri?uoride. foregoing compounds, those wherein the group IV-A 10 metal is lead or tin, the group Vlll metal is iron or Example XXVII nickel, and the organo radical is cyclopentadienyl or in A base stock is prepared by mixing 24 volumes of iso denyl or a substitution product thereof, are preferred pentane, 66 volumes of isooctane, and 10 volumes of because of their case of preparation and because of their cunrene. To this base stock is added 0.75 gram of lead high eifectiveness as antiknock and antiwear agents. Par per gallon as a mixture (296.0 parts) containing 5.5 ticularly preferred compounds, for the reasons given percent of tetramethyllead, 24 percent of trimethylethyi above, include bis(indenyliron dicarbonyl)diphenyltin, lead, 37.5 percent of dimethyldiethyllead, 26 percent of cyclcpentadienylnicxel carbonyl methyllead dichloride, methyltriethyllead and 7 percent of tetraethyllead. To and methylcyclopentadienylnickel carbonyl trimethyltin. the resulting mixture are added 79.1 parts (0.70 theory) in making the valuable compounds of this invention, of 1,2-dichloropropane and 145.6 parts (0.775 theory) 20 a Wide variety of reactants are available. The alkali of ethylene dibromide. Finally, 0.3 gram of lead per metal simple or substituted cyclopentadienyliron (or other gallon as bis(cyclopentadienyliron dicarbonyl)dimethyl group Vlll metal) carbonyl is made by the reaction of lead is added. A signi?cant increase in knock rating the appropriate cyclopentadienyl groupVllI metal car accompanies the ?nal addition. bonyl monomer or dimer with the alkali metal amalgam in tetrahydrofuran or other suitable solvent. The mix Example XXVHI ture is stirred at room temperature until the reaction is When the base stock of Example XXVII is treated with essentially complete. The reaction mixture, after removal 1.5 grams of tin per gallon, as bis(cyclopentadienyliron of the mercury, is then used without further treatment dicarbonyl)diphenyltin, an increase in knock rating is ob for the reaction of the invention. Illustrative of these served. 30 compounds are cyclopentadienyliron dicarbonyl lithium, Example XXIX methylcyclopentadienylcobalt carbonyl disodiunr, diethyl A tetraethyllead ?uid is prepared by mixing 323.5 parts cyclopentadienylnicke] carbonyl potassium, indenylpal‘ of tetraethyllead with 144.8 parts (0.60 theory) of n-hexyl ladium carbonyl rubidium and ?uorenylplatinum carbonyl chloride and 156.2 parts (0.625 theory) of mixed dibromo cesium. toluenes. The resulting ?uid is mixed with a su?icient Methods for the preparation of organometal halides—— amount of a {base fuel consisting of 15 percent by volume the other reactants in the metathetic process of this in of alkylate gasoline and 85 percent of catalytically cracked vention-are described by E. Krause and A. von Grosse gasoline to give a lead concentration of 1.25 grams of in “Die Chemie der Metallortzanischen Verbindungen,” lead per gallon. Borntraeger, Berlin, 1937. Further examples of such The addition to this blended fuel of ‘ compounds include triphenylitin chloride, dimethyltin di 0.3 gram of tin per gallon as bis(cyclopentadienyliron chloride, triphenyllead chloride, diethyllead dichloride, dicarbonyl)dimethyltin increases the antiltnock value ?ill‘i'l?tilyilll'l difluoride, tris(ethylcyclopentadienyl)ger thereof. manium iodide, bis(dodecyclopentadienyl)germanium di The following examples serve to illustrate the antiwear bromide, bis(ethylphenyl)tin dichloride and bis(acetyl utility of the compounds of this invention. All percent— c. ages given in these examples are by Weight. cyclohexyDlead dibromide. The reactants used in the preparation of the compounds Example XXX of this invention can be employed in a wide variety of A Mid-Continent solvent-extracted mineral oil not con proportions. in the metathesis reaction the proportions taining an additive of the invention is run in a four-ball ;. can range from a 100 percent or greater excess of the wear machine using 1/2 inch SAE 52—100 steel balls, at carbonyl reactant to ‘a 100 percent or greater excess of a speed of 570 rpm. for 2 hours and under a load or" the organometal halide reactant, but the proportions 10 kilograms. Following the test, the balls are disas chosen are largely determinative of the nature of the sembled and the average scar diameter‘ on the lower three product. Thus, the use of an excess of the carbonyl re~ actant favors ‘a product containing little or no halogen, balls is measured. The test is then repeated with the addi~ in St tion to the mineral oil of 2 percent by weight of cyclo whereas the use of an excess of the organometal halide pentadienyliron dicarbonyl tripheny tin. The average scar reactant favors a product containing both organc groups diameter in the second case is less than that in the ?rst. and halogen ‘groups attached directly to the group IV-A metal. In the hydrohalogenation reaction the propor Example XXX! tions can range from a 100 percent or greater excess of To the Mid-Continent oil of Example XXX is added the carbonyl reactant to a 100 percent or greater excess 1.5 percent of cyclopentadienylnickel carbonyl triphenyl of hydrogen halide; the greater the relative proportion tin. This addition results in a marked diminution in wear of hydrogen halide, the greater is the proportion of halo~ as tested by the four-ball Wear machine. gen and the smaller the proportion of organo group or As indicated above, a Wide variety of organobimetallic groups attached directly to the group IV-A metal in the compounds falls Within the scope of this invention. Fur product. Usually the reactants are employed in propor ther examples of these compounds are the following: tions corresponding approximately to stoichiometric cyclopentadienylcobalt carbonyl bis(tribenzylgermani~ equivalents but a moderate excess of one reactant or the urn), bis(methylcyclopentadienylnickel carbonyl) ,dipro other is often used to bring about an increased reaction pyltin, tris(dimethylcyclopentadienylruthenium dica'r 70 rate. bonyl)lead ?uoride, indenylrhodium carbonyl dimethyltin, Among the criteria for the choice of solvents to be em ?uorenylpalladium carbonyl ethyllead ‘dichloride, bis ployed in the reactions of this invention are that ‘the sol (cyclopentadienylosmium dicarbonyl)germanium dibro vents bc liquid under the reaction conditions and that mide, ethylcyclopentadienyliridium carbonyl ethyltin chlo they be inert to both reactants and products. Accord ride, bis(indenylplatinum carbonyl)diethyllead, tris(llu ingly, the solvents may include in general ‘aromatic hy 3,069,449 11 12 drocarbons such as benzene, toluene, the xylenes and the phosphate, etc.), boron additives, corrosion inhibitors, de> like; aliphatic such as hexanes, heptanes, tergents, antiicing additives, other antiknock agents (e.g., octanes, petroleum naphtha and the like; aliphatic or are methylcyclopentadienylmanganese tricarbonyl, cyclo matic ethers such as diethyl ether, diethylene glycol diethyl pentadienylmanganese tricarbonyl, cyclopentadienylnickel ether, diethylene ‘glycol ‘dibutyl ether or tetrahydrofuran; nitrosyl, manganese pentacarbonyl, iron carbonyl, dicycloi aliphatic alcohols such as methanol, ethanol, isop-ropanol, pentadienyliron), induction system cleanliness additives, the pentanols, etc., and halohydrocarbons such as methyl top cylinder lubricants and the like. ene chloride and carbon tetrachloride, and the like. The Having thus described the process and novel products preferred solvent is tetrahydrofuran because of its rela of this invention it is not intended that it be limited except tively high solubility for the reactants and for the other 10 as set forth in the following claims. reasons mentioned ‘above. I claim: The reactions of this invention may be carried out at 1. A compound represented by the general formula any temperature within the normal liquid range of the LRMKCO)a]bM4R’4_b_cXc, wherein R is a radical se solvent or at higher temperature if the liquid phase is lected from the group consisting of cylopentadienyl, maintained by the application of pressure. Room tem alkylcyclopentadienyl and acylcyclopentadienyl radicals perature is perf ctly satisfactory in most instances be containing from 5 to about 18 carbon atoms and of cause of the high reaction rate but temperatures slightly indenyl and ?uorenyl radicals; R’ is a radical selected above room temperature may be desirable in certain in from the group consisting of alkyl, aryl, cycloalkyl, stances for reactions involving the higher alkyl deriva aralkyl, alkaryl, and alkenyl radicals containing from 1 tives. Thus, temperatures in the range of ‘0 to 150° C. 20 to about 18 carbon atoms; M4 is an element of group and higher are employable although best results are ob iV-A of the periodic system having an atomic number tained between 25 and 75° C. and this range is therefore from 32 to 82, inclusive; M8 is an element of group VIII preferred. of; the periodic system having an atomic number from Because the reactions usually proceed rapidly under 26 to 78, inclusive; X is a halogen; a is 1 when M8 is temperatures obtainable at normal pressure, atmospheric O an element selected from the group‘ consisting of cobalt, pressure is usually satisfactory, but pressures ranging nickel, rhodium, palladium, iridium and platinum and from 10 mm. Hg to 100 atmospheres may be used if de is 2 when M8 is an element selected from the group con sired. sisting of iron, ruthenium and osmium; b is an integer The reactions of this invention may be carried out un from 1 to 3, inclusive; 0 is an integer from 0 to 3, in der any atmosphere inert to both reactants and products. 30 clusive; and the sum of b and c is less than 5. The lead and tin compounds are stable on exposure to dry 2. The compound of claim 1 wherein M4 is tin. air, which can thus be used with safety. The use of dry 3. The compound of claim 1 wherein M4 is tin and nitrogen is preferred for the less stable germanium com M8 is iron. pounds and for the preparation of the alkali metal-con 4. Cyclopentadienyliron dicarbonyl triphenyltin. taining carbonyl reactants. Other suitable protective at 5. Bis(cyclopentadienyliron dicarbonyl)dimethyltin. mospheres include gaseous saturated hydrocarbons such 6. Bis(cyclopentadienyliron dicarbonyhdiphenyltin. as and ethane and the noble gases helium, neon, 7. Cyclopentadienyliron dicarbonyl tin trichloride. argon, krypton and . 8. The method of preparing a compound represented The normally solid compounds of this invention are by the general formula [RM8(CO),,]bM4R'4_b_cXc, soluble in and can be puri?ed by recrystallization from a 40 wherein R is a radical selected from the group consisting variety of organic solvents. Speci?cally, simple aromatic of cyclopentadienyl, alkylcyclopentadienyl, and acylcy solvents such -as benzene or toluene, simple aliphatic sol~ clopentadienyl radicals containing from 5 to about 18 vents such as hexane, alcohols such as ethanol and halo carbon atoms, and of indenyl and ?uorenyl radicals; R’ hydrocarbons such as methylene chloride, and their mix is a radical selected from the group consisting of alkyl, tures, are found to be satisfactory. aryl, cycloalkyl, aralkyl, alkaryl, and alkenyl radicals In the improved fuels of this invention, organic halide 4:5 containing from 1 to about 18 carbon atoms; M4 is an scavengers can be employed. These scavengers can be element of group IV-A of the periodic system having an either aliphatic or aromatic halohydrocarbons or a com atomic number from 32 to 82, inclusive; M8 is an ele 1 bination of the two having halogen attached to carbon in ment of group VIII of the periodic system having an either the aliphatic or aromatic portion of the molecule. atomic number from 26 to 78, inclusive; X is a halogen; These scavengers may also be carbon-, hydrogen-, and 50 a is 1 when M8 is an element selected from the group oxygen-containing compounds such as haloalkyl ethers, consisting of cobalt, nickel, rhodium, palladium, iridium halohydrins, halonitro compounds, and the like. Still and platinum, and is 2 when M8 is an element selected othervexamples of scavengers that may be used in this from the group consisting of iron, ruthenium and invention are illustrated in US. Patents 1,592,954; 1,668, osmium; b is an integer from 1 to 3, inclusive; 0 is an 022; 2,398,281; 2,479,900; 2,479,901; 2,479,902; 2,479, integer from 9 to 3, inclusive; and the sum of b and c 903; 2,496,983; 2,661,379; 2,822,252; 2,849,302; 2,849, is less than 5, which comprises reacting a compound rep— 303 and 2,849,304. Mixtures of different scavengers may resented by the general formula RM8(CO)aM1d, where also be used. Concentrations of organic halide scavengers in M1 is an element of group I—A of the periodic sys~ ranging from about 0.2 to about 2.5 theories based on the tem having an atomic number from 3 to 55, inclusive; 60 lead ‘are usually su?icient although greater or lesser a is 1 when M8 is an element selected from the group amounts may be used. Thus, in general, use is made of consisting of cobalt, nickel, rhodium, palladium, iridium an amount of organic halide scavenger that is capable of and platinum, and is 2 when M8 is an element selected reacting with the lead during engine combustion to form from the group consisting of iron, ruthenium and osmium; relatively volatile lead halide and thereby effectively to and d is 1 when M8 is an element selected from the control the amount of deposit formed in the engine. 65 group consisting of iron, nickel, ruthenium, palladium, The fuels of this invention can contain other additives. osmium and platinum and is 2 when M8 is selected from Typical of these are antioxidants (e.g., N,N’-di-sec-butyl the group consisting of cobalt, rhodium and iridium, with p-phenylenediamine; p-N—butylamino ; 4-methyl a compound represented by the general formula 2,6-di-tert-butyl phenol; etc.), metal deactivators (e.g., R'4—b—cM4Xb+c N,N’-disalicylidene-1,2-diaminopropane, etc.), dyes, phos wherein Z), c, R, R’, M1, M4, M8 and X have the mean phorus additives (e.g., tris(B-chloropropyl)thionophos ings de?ned hereinbefore. phate, dimethyltolyl phosphate, dimethylxylyl phosphate, 9. The method of claim 8 wherein M1 is sodium and dicresyl phosphate, cresyldiphenyl phosphate, trimethyl X is chlorine. phenyldimethyl phosphate, tricresyl phosphate, phenyl 10. The method of preparing cyclopentadienyliron di 3,069,449 13; 14 carbonyl triphenyltin which comprises reacting cyclo osmium; b is an integer from 1 to 3, inclusive; 0 is an pentadienyliron dicarbonyl sodium with triphenyltin chlo integer from O to 2, inclusive; e is an integer from 1 to ride. 3, inclusive; and the sum of b, c and e is less than 5, 11. The method of preparing bis(cyclopentadienyl which comprises reacting a compound represented by the iron dicarbonyl)dimethyltin which comprises reacting 5 general formula [RM3(CO),,]bM4R’4_b_cXc, wherein a, cyclopentadienyliron dicarbonyl sodium with dimethyltin b and c have the meanings de?ned hereinbefore, with a dichloride. hydrogen halide. 12. The method of claim 8 wherein M4 is tin and M8 16. The method of claim 15 wherein X is chlorine. is iron. 17. The method of claim 15 wherein M4 is tin and M8 13. The method of claim 8 wherein the reaction is car 10 is iron. ried out in an inert organic solvent. 18. The method of preparing cyclopentadienyliron di 14. The method of claim 8 wherein the reaction is carbonyl tin trichloride which comprises reacting cyclo carried out in tetrahydrofuran as solvent. pentadienyliron dicarbonyl triphenyltin with hydrogen 15. The method of preparing a compound represented chloride. by the general formula [RM3(CO)a]bM4R’4_b_c_eXc+e, 19. The method of claim 15 wherein the reaction is wherein R is a radical selected from the group consisting carried out in an inert organic solvent. of cyclopentadienyl, alkylcyclopentadienyl and acylcyclo 20. The method of claim 15 wherein the reaction is pentadienyl radicals containing from 5 to about 18 car carried out in methylene chloride as solvent. bon atoms, and of indenyl and ?uorenyl radicals; R’ is a radical selected from the group consisting of alkyl, References {liter-l in the ?le of this patent aryl, cycloalkyl, aralkyl, alkaryl, and alkenyl radicals UNITED STATES PATENTS containing from 1 to about 18 carbon atoms; M4 is an element of group IV—A of the periodic system having an 3,007,953 Closson et al. ______Nov. 7, 1961 atomic number from 32 to 82, inclusive; M8 is an ele 3,015,668 Kozilowski ______Jan. 2, 1962 ment of group VIII of the periodic system having an FOREIGN PATENTS atomic number from 26 to 78, inclusive; X is a halogen; a is 1 when M8 is an element selected from the group 793,355 Great Britain ______Apr. 16, 1958 consisting of cobalt, nickel, rhodium, palladium, iridium OTHER REFERENCES and platinum, and is 2 when M8 is an element selected King et al.: “Chem. and Industry,” pp. 747—748 (June from the group consisting of iron, ruthenium and 3, 1961). UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,069,449 December 18, 1962 Richard D, Gorsich It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 61, for "peroidien read ~— periodic ~——; column 4, lines 74 and 75, for "cryclopentadienyl" read m» cyclopentadienyl ——;; column 5, lines 64 and 65, for "methathesis" read —— metathesis ——; column 6, line 5, for "as" read -— at --~g column 10, line 43, for "(d0decyclopentadienyl)" read -»~ (dodecylcyclopentadienyl) “w; column 11, line 74, strike out "dicresyl phosphate, cresyldiphenyl phosphate, trimethyl", and insert same after "phe-nylJ in line 75, same column 11 o Signed and sealed this 17th day of September 1963, (SEAL) Attest:

ERNEST w. SWIDER DAVID L- LADD Attesting Officer Commissioner of Patents