US3105084A - Norbornadiene metal compounds and process for same - Google Patents

Description

United States Patent 3,195,084 NURBORNADENE METAL COMPOUNDS AND PROCESS FOR SAME Geoffrey Wilkinson, London, England, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Oct. 7, 1960, Ser. No. 61,160 11 Claims. (Cl. 26042.9)

This invention relates to norbornadiene-transition metal compounds of the metals of group VIII and IB of the periodic table. This invention also relates to the preparation of these compounds by reaction of norbonadiene and a salt of a group VII-1B transition metal.

An object of this invention is to provide norbonadienetransition metal complexes of the metals of group VIII-IB of the periodic table. A further object is to provide a method for preparing these compounds by reacting a group VIII-1B transition metal salt with norbornadiene or a norbornadiene derivative. Further objects will become apparent from a reading of the specification and claims which follow.

The compounds of my invention are of three general types. The first type of compound can be termed a 1:1 complex which contains one mole of a norbornadiene compound and one mole of a transition metal salt. These compounds are formed by reaction of a transition metal salt of the iron sub-group e.g. iron, ruthenium and osmium or the nickel sub-group, e.g., nickel, palladium and platinum with a norbornadiene compound. A further type of compound within the scope of my invention may be termed a bis(1:1) compound. These compounds are dimeric and are formed by reaction of one mole of a norbornadiene compound with one mole of a transition metal salt. The metals of the cobalt sub-group of the periodic table, e.g., cobalt, rhodium and iridium form such compounds. A still further type of compound within the general scope of my invention may be termed 1:2 compounds indicating that the compounds contain one mole of a norbornadiene compound and two moles of a transition metal salt. The metal salts of group IB metals, e.g., copper, silver and gold, react with norbornadiene to form such compounds.

lThe compounds of the invention are, in general, stable organometallic compounds. They are diarnagnetic and have a number of utilities. In general, the compounds contain a relatively high quantity of metal per molecule and therefore are excellent sources of the metal for use in chemical processes.

Many of the compounds may be used as fuel additives to residual and distillate fuels such as those employed in home heater fuels, diesel fuels, and jet fuels. In this use, the additive serves to reduce smoke and/ or soot formation on combustion of the fuel. Further, my compounds may be added to hydrocarbon fuels of the gasoline boiling range for use in an internal combustion engine. In this use, my compounds act as an antiknock agent. In addition, many of my compounds are useful additives to various hydrocarbon lubricants to improve their lubricity. Another use for my compounds is as a metal source in gas phase metal plating. A still further use for my compounds is as additives to solid propellants to control burning rate.

The norbornadiene compound (a hydrocarbon containing a bicyclo(2:2:l)-hepta-2:5-diene ring) which isa reactant in my process may be substituted with hydrogen or hydrocarbon substituents such as alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkaryl groups and aralkyl groups. Preferably, the norbornadiene reactants which I employ contain from 7 to about carbon atoms. The simplest norbornadiene which I employ is the compound bicyclo(2:2:l)-hepta-2:5-diene.

Patented Sept. 24, 1963 Similar compounds which may be employed are methyl bicyclo(2:2:l)-hepta-2:5-diene, phenyl bicyclo(2:2:l)- hepta-2z5-diene, benzyl bicyclo (2:2:1)-hepta-2:5-diene, tolyl bicyclo(2:2:l)-hepta-2:5-diene, butenyl bicyclo- (2z2:1)-hepta-2:5-diene,' and the like.

The transition metal saltswhich are the other reactant in my process are salts of the group VIII-1B transition metals which preferably are soluble to some degree in polar solvents. Typical of such salts are the cyanides, halides, nitrates, sulfates, acetates, phosphates, phosphites, and the like. Preferred transition metal salts which are employed in my process are the transition metal halides of the group VIIIIB metals.

My process comprises the mixing together of the norbornadiene compound and a group VIII-1B transition metal salt, both as defined above. customarily a solvent is employed although the nature of the solvent is not critical. The preferred solvents are polar in nature such as water, ethanol, ether, chloroform, and the like. The temperature and pressure employed in the reaction are not critical and the process goes well at room temperature and atmospheric pressure. Agitation of the reaction mixture may be employed although this is not necessary. In some cases, the process can be carried out under a blanketing atmosphere of an inert gas which protects both the reactants and products from oxidation. 7 Since the products obtained from my process are generally solids, the means employed for separation of product involve crystallization, filtration, etc. In other words, the products can be separated by the customary methods employed to separate solid products from a generally liquid reaction medium.

To further illustrate the compounds of the invention and their mode of preparation, there are presented the following examples in which all parts and percentages are by weight unless otherwise indicated.

Example I To 2.82 parts of norbornadiene were added 1.36 parts of silver nitrate in 10 parts of water. The mixture was agitated at room temperature for five minutes, and the white solid complex which formed was filtered off and recrystallized from ethanol to give 0.95 parts of norbornadiene-bis(-silver nitrate). Analysis: Found: C, 19.4; H, 2.4; Ag, 50.2. C I-I (AgNO requires: C, 19.5; H, 1.9; Ag, 50.0 percent. Norbornadiene-bis(silver nitrate) decomposes in water giving off a strong smell of norbornadiene. The compound also decomposes on standing in the air or on warming. It is soluble in warm ethanol, carbon tetrachloride, chloroform and benzene, but it is almost insoluble in acetone, ether and light petroleum.

Example 11 To 2.6 parts of cupric bromide in 23.7 parts of ethanol was added 4.55 parts of norbornadiene. The mixture was agitated for five minutes. The white crystalline product formed was removed by filtration and washed with 3.94 parts of ethanol and 3.52 parts of ether to give 1.4 parts of norbornadiene-bis(cuprous bromide). Found: C, 19.8; H, 2.6 and Cu, 32.8. C H (CuBr) requires: C, 22.2; H, 2.1 and Cu, 33.5 percent. The compound remained as a fine, White crystalline solid which slowly turned green on standing in air. The compound readily lost norbornadiene at reduced pressure to leave cuprous bromide, and was decomposed in water to give cuprous oxide. Norbornadiene-bis(cuprous bromide) is practically insoluble in all common organic solvents.

Example III To 1.82 parts of norbornadiene were added one part of platinic chloride and 10.5 parts of glacial acetic acid. The reaction mixture was agitated for 15 minutes after which a brown solid which formed was filtered oil and ethanol.

fine, white crystals which decomposed at a temperature between 230-280 C. and were somewhat soluble in acetic acid, chloroform and acetone.

Example IV To 1.1 parts of dibenzonitrile palladium dichloride in 52.5 parts of chloroform were added 3.64 parts of norbornadiene. The mixture was allowed to stand for one hour after which the yellow deposit formed was filtered oh and washed with chloroform and light petroleum. After recrystallization from glacial acetic acid, the product was washed with methanol and acetone and vacuum dried to give 0.58 parts of norbornadiene palladium dichloride. Found: C, 31.4 and H, 3.6. CqHgPdClz requires: C, 31.2 and H, 3.0 percent. The compound was obtained as yellow needles which decomposed at temperatures between 190-200 C.

Using a procedure similar to that employed in Examples III and IV, the product methyl norbornadiene-nickel dichloride is prepared in good yield.

Example V To 1.03 parts of ruthenium trichloride (a commercial mixture of hydrated triand tetra-chlorides) was added 31.6 parts of ethanol to form a solution which was centrifuged to remove insoluble material. The clear redbrown solution was shaken with 3.64 parts of norbornadiene and allowed to stand for 25 hours. The red product was washed repeatedly with acetone to remove ruthenium chlorides. There was obtained 0.6 parts of norbornadiene ruthenium dichloride. Found: C, 31.6; H, 3.9 and Cl, 27.5. C H RuCl requires: C, 31.8; H, 3.1 and Cl, 26.8 percent. The compound was diamagnetic and insoluble in water and all common organic solvents.

Example VI To 1.1 parts of ruthenium chloride, as defined in the previous example, was added 31.7 parts of acetone to form a solution. The solution was centrifuged to remove any insoluble material. To the clear solution was added four parts of lithium bromide, and the resulting solution was filtered and added to 3.64 parts of norbornadiene and allowed to stand for 24 hours. The precipitate was washed repeatedly with acetone and then vacuum dried to give 0.6 parts of nor-bornadiene ruthenium dibromide. Found: C, 23.2 and H, 2.8. CqHgRUBI'z requires: C, 23.8 and H, 2.3 percent. The compound was a darkbrown solid which is insoluble in all common solvents.

The products butyl norbornadiene iron dichloride and nor'oornadiene osmium dibromide are prepared in good yield according to the procedure employed in Examples V and VI by reaction of butyl norbornadiene with ferric chloride and the reaction of norbornadiene with osmium tribromide.

Example VII To 0.7 parts of rhodium trichloride (commercial mixture of hydrated triand tetra-chlorides) was added 1.82 parts of norbornadiene in about 8 parts of aqueous The mixture was agitated for two days. The yellow deposit which formed was recrystallized from hot chloroform/light petroleum to give 0.62 part of norbornadiene rhodium chloride which decomposed at 240 C. Found: C, 37.3; H, 3.7; Rh, 45.3; C1, 15.5 percent with a molecular weight of 481 (ebullioscopic in benzene). (C7H3RhC1)2 requires: C, 36.5; H, 3.5; Rh, 44.6; C1, 15.4 percent with a molecular weight of 462. The compound forms as fine-yellow crystals which are soluble in chloroform and benzene but are almost insoluble in ether and light petroleum.

dib-romide and p-toluidine.

By a similar process to that employed in Example VII, 7

dimeric compounds containing the basic structural-unit norbornadiene cobalt chloride and norbornadiene iridium bromide are prepared in good yield.

The compounds of my invention may be employed in various chemical reactions with nitrogen-containing compounds such as pyridine tand p-toluidine. This use is illustrated by means of the following Examples VIII and 1 IX in which all parts and percentages are by weight unless otherwise indicated.

Example VIII To 0.39 parts of norbornadiene ruthenium dichloride, prepared as in Example V, was added 14.75 parts of pyridine, and the resulting mixture was heated at 120 C. for 45 minutes. On cooling, the resultant red solution gave a red crystalline product. Recrystallization from chloroform/ light petroleum gave 0.3 parts of tetrapyridine ruthenium dichloride. Found: C, 49.4; H, 4.3; N, 11.4; C1, 14.8 percent with a molecular weight of 487 (ebullioscopic in benzene). Calculated for C H Cl N Ru: C, 49.1; H, 4.3; N, 11.5; C1, 14.5 percent and a molecular weight of 489. a

Example IX To 0.29 parts of norbornadiene ruthenium dichloride, prepared as in Example V, was added 0.8 parts of p-toluidine. The mixture was fused and held at a temperature of C. for 30 minutes. After being cooled, the red solid residue was washed with ether and dichloromethane to yield a yellow crystalline solid which, on vacuum drying, gave noroornadiene-bis(p-toluidine) ruthenium dichloride (0.2 parts). Found: C, 53.1; H, 5.4; N, 6.2 and Cl, 14.7. C H N Cl Ru requires: C, 52.6; H, 5.5; N, 5.9 and Cl, 14.8 percent. The compound is insoluble in chloroform.

In a similar manner to that employed in Example IX, the compound, norbornadiene-bis(p-toluidine) ruthenium dibromide, was prepared from norbornadiene ruthenium Found: C, 45.0; H, 5.1; N, and BI, 27.9. C21N25N2BI'2RH requires: C, H, 4.6; N, 4.9 and Br, 28.2 percent.

The compounds of the invention have a variety of uses. Many, for example, are useful as additives to hydrocarbon fuels and lubricants. For example, many of them, when added to a hydrocarbon fuel of the gasoline boiling range, are found to increase the octane number of the fuel. The compounds may be added to gasoline along with halo'hydrocarbon scavengers such as ethylene dichloride and ethylene dibromide, phosphorus ignition control compounds such as tricresyl phosphate, and other antiknock agents such as tetrethyllead, methylcyclopentadienyl manganese tricarbonyl andthe like. They are also useful as additives to jet fuels, home heater fuels and diesel fuels to reduce smoke and/ or soot formation on combustion of the fuels. In addition, my compounds may be employed as additives to lubricating oils to improve their characteristics. A still further utility for my compounds is as additives to solid propellants to control the burning rate of the propellant.

The compounds may also be used as metal plating agents. When so employed, they are decomposed at elevated temperatures so as to lay down a metallic film on a substrate material. Preferably, the plating operation is carried out in the presence of an inert gas so as to prevent oxidation of the metal coating or substrate material during the plating operation. The metal films, for example, may be employed to produce a decorative efiect on the substrate material, to increase its resistance to corrosion, and to form a conductive surface. In the latter application, the compounds can be employed in forming printed circuits by decomposing the organometallic compound so that it lays down an electrically conductive metallic film on a substrate surface that is covered by a stencil.

Deposition of metal on a glass 'cloth illustrates my process which employs the compounds of the invention in gas phase metal plating. A glass cloth band weighing one gram is dried for one hour in an oven at 150 C. It is then placed in a tube which is devoid of air and there is added to the tube 0.5 grams of norbornadiene ruthenium dibromide. The tube is heated at 400 C. for one hour after which time it is cooled and opened. The cloth has a uniform metallic grey appearance and exhibits a gain in weight of about 0.02 gram. Thus a cloth is prepared in which the individual fibers are coated with a layer of ruthenium.

Having described my novel compounds, their mode of preparation and their many utilities, I desire to be limited only within the lawful scope of the appended claims.

I claim:

1. Compounds containing 1 mole of a norbornadiene hydrocarbon compound containing from 7 to about 15 carbon atoms, said norbornadiene compound being bonded to a transition metal salt selected from the class consisting of inorganic iron-subgroup metal halides and nitrates and inorganic nickel-subgroup metal halides and nitrates.

2. Dimeric compounds containing as the basic unit one mole of a norbornadiene hydrocarbon compound bonded to one mole of a salt, said norbornadiene compound containing from 7 to about 15 carbon atoms and said salt being selected from the class consisting of inorganic cobalt-subgroup metal halides and nitrates.

. Norbornadiene platinum dichloride.

. Norbornadiene palladium dichloride.

. Norbornadiene ruthenium dichloride.

. Norbornadiene ruthenium :dibromide.

. Noribornadiene rhodium chloride dimer.

Process comprising reacting a norbornadiene hydrocarbon compound cont-aining from 7 to about 15 carbon atoms with a salt selected from the class consisting of inorganic group VIII metal halides and nitrates and dibenzonitrile group VIII metal halides.

9. Process for the preparation of norbornadiene platinum dichloride, said process comprising reacting norbornadiene with platinic chloride.

10. Process for the preparation of norbornadiene palladium dichloride, said process comprising reacting dibenzoni-trile palladium dichloride with norbornadiene.

11. Process for the preparation of nor-bornadiene ruthenium dibromide, said process comprising reacting ruthenium dibromide with norbornadiene.

References Cited in the file of this patent Alexander et al.: J.A.C.S., 82 (Feb. 5, 1960), pp. I

Traynham et al.: J.A.C.S., 81 (Feb. 5, 1959), pp. 571-574.

Claims (1)

1. COMPOUNDS CONTAINING 1 MOLE OF A NORBORNADIENE HYDROCARBON COMPOUND CONTAINING FROM 7 TO ABOUT 15 CARBON ATOMS, SAID NORBORNADIENE COMPOUND BEINF BONDED TO A TRANSITION METAL SALT SELCTED FROM THE CLASS CONSISTING OF INORGANIC IRON-SUBGROUP METAL HALIDES AND NITATES AND INOGANIC NICKEL-SUBGROUP METAL HALIDES AND NITRATES.