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3,088,963 United States Patent Office Patented May 7, 1963 2 compound is reduced to a single bond thus making four 3,088,963 electrons available for bonding to the two nickel atoms. MANUEFACTURE OF CYCLOPENTADENYL Each of the carbon atoms on either side of the triple bond NICKELNETROSYL COMPOUNDS is thereby bonded to each of the nickel atoms. The Michael Dubeck, Royal Oak, Mich., assiga or to Ethyl Cor actual configuration of the bridging acetylenic molecule poration, New York, N.Y., a corporation of Delaware is believed to be approximately at right angles to the No Drawing. Fited Sept. 12, 1960, Ser. No. 55,181 plane in which the two inter-connected nickel atoms lie. 6 Claims. (C. 260-439) This is shown in the above formula by means of the This invention relates to novel organometallic com dotted lines indicating bonding of the carbon atom which pounds and a process for their preparation. More speci O is behind the plane of the paper to the two nickel atoms fically, this invention relates to cyclomatic nickel nitrosyl illustrated as lying in the plane of the paper. The other compounds. carbon atom which is bonded to the two nickel atoms is It is an object of this invention to provide a novel proc depicted as lying in front of the plane of the paper. Thus, ess for the preparation of cyclomatic nickel nitrosyl com the bonds between this carbon atom and the two nickel pounds. A further object is to provide novel compounds atoms are drawn as solid lines. produced by this process. Additional objects will be The substituent groups Q and Q', as shown in the above come apparent from a reading of the specification and formula, may be the same or different and are hydrogen claims which follow. or univalent hydrocarbon groups containing from one to The objects of this invention are accomplished by pro about 10 carbon atoms. Q and Q are preferably alkyl viding a process in which compounds having the formula 20 groups such as methyl, ethyl, propyl, butyl, amyl, octyl QC=CQ'. CyNiNiCy’ are reacted with a nitrosylating or decyl, including normal alkyls or branched chain agent to form compounds having the formulae CyNiNO alkyls. Preferably, Q and Q, if an alkyl group, contains and Cy'NiNO. The compounds, CQ=CQ-CyNiNiCy', from one to about six carbon atoms since alkyl radicals are fully described in my prior U.S. application Serial No. within this range impart desirable physical properties 852,216, filed November 12, 1959. As shown in that ap 25 to the compounds of my invention. plication, these compounds are believed to have the struc Q and Q may also be an aryl radical, either a fused or tural formula as follows: single ring, such as phenyl, tolyl, xylyl, naphthyl or the like. In addition, Q and Q may be hydrocarbon groups Q X Q containing unsaturated double bonds such as alkenyl or cy 30 cloalkenyl radicals. Typical of such radicals are butenyl, CyN - Ni Cy’ pentenyl, hexenyl, nonenyl, cyclohexenyl, cyclopentenyl In this formula, Q and Q' represent either hydrogen or and the like. In addition, the Q groups may be alkaryl univalent hydrocarbon radicals containing from one to radicals, aralkyl radicals, and cycloalkyl radicals contain about 10 carbon atoms. Cy and Cy represent cyclomatic ing up to about 10 carbon atoms. Typical of such radi hydrocarbon groups which donate five electrons to the 3 5 cals are benzyl, phenylethyl, phenylpropyl, phenylbutyl, nickel atoms for bonding. By viture of the electrons cyclohexyl, cyclopentyl, cycloheptyl, cyclodecyl, p-ethyl donated to each of the nickel atoms from the cyclomatic phenyl, m-butylphenyl, p-methylphenyl and the like. hydrocarbon groups, the acetylene molecule and the other Although the Q groups, as defined above, are univalent nickel atom, each of the nickel atoms achieves the inert hydrocarbon radicals or hydrogen, these groups may be gas electron configuration of krypton. 40 substituted with polar substituents which preferably The cyclomatic hydrocarbon groups, designated by the should be separated by at least two carbon atoms from symbols Cy and Cy' in the above formula, may be the the triple acetylenic bond to avoid cumbersome side reac same or different and are cyclopentadienyl-type hydrocar tions. Typical acetylenic compounds containing such bon radicals. By this, it is meant that the radical con non-reactive non-hydrocarbon Substituent groups are per tains the cyclopentadienyl moiety. In general, such cy 45 halo butynes, propargyl alcohol, ethynyl cyclohexanol, clomatic hydrocarbon groups can be represented by the beta carboxy esters of the butynes, pentynes, hexynes, and formulae: heptynes, 5-methoxypentyne-1, and the like. The reactant, QC=CO'CyNiNiCy', as described i. R above, is reacted with a nitrosylating agent according to 50 the process of my invention. A variety of nitrosylating agents such as, for example, nitric oxide, an alkali metal thY R- N/6 7 l nitrite such as sodium or potassium nitrite, or a nitroso Rs substituted aromatic compound such as N-methyl-N- wherein the R's are selected from the group consisting of nitroso-p-toluene sulfonamide may be employed. Prefer hydrogen and univalent hydrocarbon radicals. ably, however, the nitrosylating agent is nitric oxide since A preferred class of cyclomatic radicals suitable in the it is comparatively cheap, readily available and, as a gas, practice of my invention are those which contain from five can be intimately mixed with the nickel reactant and to about 13 carbon atoms. These are exemplified by cy thereby give an especially high yield of product. My clopentadienyl, indenyl, methylcyclopentadienyl, propyl process can be carried out at temperatures from about cyclopentadienyl, diethylcyclopentadienyl, phenylcyclo 60 zero to about 100° C. Preferably, however, my process pentadienyl, tert-butyl cyclopentadienyl, p-ethylphenyl cy is carried out between about 20 to about 30° C. since clopentadienyl, 4-tert-butyl indenyl and the like. The within this temperature range yields are maximized, and compounds which yield these radicals are preferred as undesirable side reactions are minimized. they are the more readily available cyclomatic com My process may be carried out under pressure if de pounds, and the compounds of my invention containing sired. In general, however, it goes well at atmospheric these radicals have the more desirable physical charac pressure. Although not essential, it is desirable to agitate teristics which render them of superior utility. the reaction mixture since this insures an even reaction As shown in the above formula, the bridging acetylene rate. In some instances, it may be desirable to employ type molecule is believed to be bonded to both of the in the reaction system a blanketing atmosphere of an nickel atoms in forming the compounds of my invention. 70 inert gas. The function of the inert gas is to shield the As visualized, the triple bond in the bridging acetylenic reaction mixture from oxidation and thereby prevent oxi 3,088,963 3 4. dation of the reactants or products. Typical of such yield of cyclopentadienyl nickel nitrosy. The yield was inert gases are nitrogen, argon, crypton and neon. 88 percent. This was determined by comparison with Nitrogen is preferred since it is cheap and readily avail standard solutions of cyclopentadienyl nickel nitrosyl able. In general, however, the nitric oxide reactant, which were run through the gas phase chromatographic which is a gas, serves as a blanketing atmosphere and 5 column. The retention time for the standard solutions thereby eliminates the need for an inert gas atmosphere. In conducting my process, it is preferable to employ and the solution obtained from my process were identical. excess quantities of the nitrosylating agent, e.g. nitric Example II oxide. The nitrosylating agent is generally considerably A solution comprising one mole of bis(cyclopentadienyl cheaper than the nickel reactant, and its use in excess O nickel) propyne dissolved in benzene is charged to a quantity assures consumption of the nickel reactant cooled reaction vessel. There are then added 1.5 moles in the process. of nitric oxide, and the reaction mixture is agitated for The products formed in my process, which are cyclo 6 hours at a temperature of 0° C. and atmospheric pres matic nickel nitrosyl compounds having the formulae, sure. The reaction product is then discharged, and ex CyNiNO and CyNiNO, are readily separated from the 5 cess solvent is stripped from the reaction product to reaction mixture by conventional means. Typical means leave an oily residue. The residue is dissolved in a of separation are chromatography, fractional distilla 30:70 (volume ratio) benzene-petroleum ether mixture tion and crystallization. and chromatographed on alumina. The eluate is relieved A preferred form of my invention involves reaction of solvent by heating in vacuo, and the residue is frac between nitric oxide and the compound, acetylene bis(cy 20 tionally distilled under reduced pressures to give a good clopentadienyl nickel). This form of my invention is yield of cyclopentadienyl nickel nitrosyl, preferred for several reasons. First, it employs reactants which are relatively cheap and readily available; the Example III acetylene bis(cyclopentadienyl nickel) compound is pre A solution comprising 0.5 mole of bis(cyclopentadienyl pared by reaction of acetylene and nickelocene. Second, 25 nickel) hexyne-3 in tetrahydrofuran is charged to a re it produces as the product the compound, cyclopenta action vessel along with one mole of nitric oxide. The dienyl nickel nitrosyl which has demonstrated utility reaction mixture is heated at 25 C. for six hours with both as a primary and supplemental antiknock. agitation. The product is then discharged, and a good My process is generally carried out in the presence yield of cyclopentadienyl nickel nitrosyl is obtained by or a solvent.