[1]United States Patent Office 312909343 3,290,343 ORGANF)NIETALLIC CG,-@IPC;UNDS CONTAINING FLUOP.OCARBON RADICALS Franc@s G. A. Stone, Watertowia, Mass., and Paul M-. Treichel, Madison, Wis., a-sigrors to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Sept' 1, i961, Ser. No. 135,462 17 Claims. (Cl. 260-429) This invention relates to novel organometallic compounds and the method for their preparation. More particularly, this invention relates to fluorocarbon Group VB to VIII metal transition compounds wherein a -CF2- group is bonded directly to the metal atom. An object of this invention is to provide a novel class of organometallic compolinds. A further object is to provide a novel class of organometallic compounds of Group VB, VIB and VIII metals wherein a iluorocarbon is bonded throu-h a -CF2-- -roup to the metal atom. A further ob,@e'et of this invention is to provide stable and useful fluorocarboil or,@anometallic compounds. An object of this invention is to provide a process of wide applicability for the preparation of novel organometallic compounds. A further obj-.ct is to provide a process for the prpparation of fiuorocarbon Group VB to VIII metal compounds which comprises reacting an ul.1- saturated fluorocarbon with a Group VB to VIII metal hydride. Other objects will become apparent from the following discussion. The objects of this invention are accomi)lished by providing organometallic compounds of Group VB to Group VIII transition metals in which one or more ffuorocarbon radicals are sigma bonded to a Group VB to VIII metal atom. The novel compounds of this invention can be represented by the formula: [Rla[R']bM[COI,[R"3P]d wherein R is a fluorocarbon radical selected from the class consisting of HCF2-CF2--, HCFC1-CF2-, HCC12-CF2-, CF3-CH=C3 R' is a cyclopentadienyl radical selected from the class consisting of -the cyclopentadienyl radical aiid hydrocarbon substituted cyclopentadienyl radicals havin.- 6 to 13 carbon atoms which enibody a ring of 5 carbon atoms having the @eneral configuration found in cyclopentadiene, M is a metal selerted from the class consisting of Groups VB, VIB, ard VIII of the Periodic Table and R" is selected from the class consistii-ig of halo,@en and alkyl, cycloalkyl, aryl, alkaryl and aralkyl hydroca@lbon radicals having from one to aboi-,t 13 carbon atoms, a, b, c, and d are integers such that a= 1 to 3, b@O to 2, c=O to 5 and d=O to 2, the values of a, b, c and d being such that the sum of all the electror-s coordir@ated to the metal and the atomic number of the metal is equal to the atomic ntimber of the next higher inert gas. Most of the fuorocarbon derivatives of the tratisition metals prepared by the process ol' this i-,ivention are air stable and unaffected by moisture, a,.id the fluorocarbon groups are only partially removed by aqueous @base or acid at elevated temperatiire. The fluorocarbon radical bonded to t-he transition metal atom in the corppounds of this inve-@ition are represented by R @.n the above formula. These fluorocarbon radicals are formed from the corresponding unsaturated fluorocarbons, tetrafluoroethylene, trifluorochloroethyiene, 1,1difluoro-2,2-dichloroethylene, 1,1,1,4,4,4-hexafluorobutyr@e-2. The process of our invent:.On coniprises the hydrometallation of these above named unsaturat.-d fluorocarbons. Generically, the process may be considered to be the adPatented Dec. 6, 1966 2 dition of metal hydride across the double bond of the unsaturated fluorinated hydrocarbon, F2C--CF2+HMn(CO)5->HF2C-CF2----Mn(CO)5 5 Specifically, oiir process is a process for the formation of the new compounds of the GroLip VB, VIB, VIIB and VIII metals of the Periodic Table which comprise reacting (a) an olefin selected from the class consisting of tetra10 fluorcethylene, trifluorochloroethylene, 1,1-difluoro2,2- dichloroethylene, and 1,1,1,4,4,4-hexafluorobutyne-2, with (b) a hydride of a Group VB, VIB, VIIB and VIH meta@l havin.- the formula 15 [R']bM[CO]e[R"3P]d[Hle wherein R' is a cyclopentadienyl radical selected from the class consistin@ of the cyclopentadienyl radical and hydrocarbon substituted cyclopentadieriyl 20 radicals having 6 to 13 carbon atoms which embody a rin- of 5 carbon atoms havin- the general configuration found in cyclopentadiene, M is a metal of Group VB, VIB, VIIB and VHI of the Periodic Table, R" is selected from the class consistii-i.- of halo.-en, aild alkyl, cycloalkyl, aryl, alkaryl, and aralkyl hydrocarbon radicals having from one to about 13 carbon atoms, b, c, d aid e are integers such that b=O to 2, c=O to 5, d=O to 2 and e=l to 3, the values of b, c, d and e bein- such that the 30 sum of all the electrons coordinated to' the metal and the atomic number of tb-- metal is equal to the atomic number of the next higher inert gas, said process being carried out at a temperature of 0 to 35 80' C., and at a pressure of 0.3 to 10 atmospheres for 5 hours to 7 days. Variables in our reaction include the starting materials; namely, the fluorinated unsaturated hydrocarbon and the rnetal hydride as well as process variables, e.g., tlie tem40 perature, pressure, time, solvent and product separation techniques. These variables are discussed in tu@-n in the paragraphs immediat-,Iy following. We have found the above named unsaturated fluorocarbons; namely, tetrafluoroethylene, trifluorochloroethylene, 1,1-di.'Iuoro-2,2-dichloroethylene and 1,1,1,4,4, 45 4-hexaffuorobutyne-2, to be the only unsaturated fluorocarbons applicable in our process. The reason Lor this is not clear, since olefins having a closely analogous structure do not yield a fluorocarbon metal r-ompound when the reaction conditions of our process are emplo3led. It 50 is rather dif@'icult, therefore, to make many generalizations as to which unsaturated fluorocarbons other than those mentio,-ied above are applicable, and it seems that our unique process is specific for the ;ibove named ofefins. Certain generalizations are possible, however, and 55 tiiey are, namely, fluorinated unsaturated hydrocarbons containing hydro,-en, aiid olefins containin@- a (CF3-C=) are not apd]icable. However, our process is applicable to a wide variety of metal hydrides. These compounds, which are appli60 -cable, fa@ll into three general classes. T-lie first of these classes are those that contain hydro.-en, a Group VB to VIII metal, and carbon monoxide. Preferred compounds of this type of metal hydride are rr@an-anese p-,ntacarbonyl hydi7id@,, rhepium p-- ntacarbon3,,I@ hy'dride, iron tetra65 carbonyl d;hydr,de, ruthenium tetracarbo.,iyl dihydr:de, osmiiim tetracaf,,,.yl d-'@hyd,ide, c.balt tetracarbonyl hydride, ruthen:illm tetracarbonyl hydride, iridium tetracarbonyl hydride, and dinickel tricarbon3rl dihydride. The 70 most preferred cojiipound of this class is manganese pentacarbonyl hydride because that cortipound is readily prepared by acidification of sodium man.-anese pentacar-
[2]bonyl (which in tum is prepared from sodium amalgam and manganese carbonyl in tetrahydrofuran) and has fairly hi.-h thermal stability -compared to most of the transition metal carbonyl hydrides. Thou,-h it is @airsensitive, it can be handled easily in a conventional high vacuum apparatus. The second class of metal hydrid-,s -applicable in our process are those t-hat contain a cyclopentadienyl radical. The cyclopentadienyl radicaldesi.-nated by the symbol R' in the formula presented above comprises a cyclornatic r,adica-1, that is, a cyclopentaetienyl moiety. In general, such cyclomatic hydrocarboii groups can be represented by the for-mulae: R3 R4 * na Ri- /^4 * 4 R2-- l@) I'J'2 where the R's are selected from the group consistin.- of hydrogen and univalent organic hy&ocarbon radicals. A preferred class,of cyclomatic radicals suitable in the practice of this invention are those which contain from 5 to about 13 carbon atoms. These are exemplified bY cyclopentadienyl, indenyl, rnethylcyclopentadienyl, propylcyclopentadienyl, diethylcyclopentadienyl, phenyleyclopentadienyl, tert-butyl cyclopentadienyll pethylphenyl cyclopentadienyl, 4-tert-butyl indenyl and the like. The compounds containin.- these radicals are preferred as they are the more readily available cyclomatic compounds and the metallic cyclomatic fluorocarbon compounds obtainable from them have the more desirable characteristics of volatility and solubility which @are prerequisites of superior hydrocarbon additives and vapor phase metal plating. The preferred compounds in this class of applicable Teactants are,cyclopentadienyl tantalurn trihydride, cyclopentadienyl chromium tricarbonyl hydride, cyclopentadienyl molybdenum, tri@earbonyl hydride, dicyclopentadienyl molybdenum dihydride, cyclopentadienyl tungsten tricarbonyl hydride, dicyclopentadicnyl tun-,Sten dihydride, dicyclopentadienyl rhenium hydride, cyclopentadienyl and iron dicarbonyl hydride. These compounds ;are preferred because of their availability and their stability under our process conditions. They generally are stable in air and consequently are easily substituted with a fluorocarbon radical by our process without elaborate precautions. The third class of metal hydride applicable in our hydrometallatio-n process include those compounds which do not contain a !cyclopentadienyl ring but which contain ligands other than a carbonyl group. These compounds are exemplified by the following list: diphenylphosphine cobalt tricarbonyl hydride, bis(diphenylphosphine)pall,adium chloride hydride, and bis(triethylphosphine)platinum chloride hydride. In these compounds the hydrocarbon radicals bonded to the phosphorus atom in the phosphine ligand can be either alkyl, cycloalkyl, aralkyl, or alkaryl radicals. Of these compounds the palladium @and platinum compounds mentioned above are most preferred because through the Lise of our process, new and useful compounds of these noble metals can be prepared. From the above diselission it is appatent that our process is applicable to a wide variety of Group VB to; VIII metal hydrides. The only limiting factor in the choice of -a suitable hydride is the thermal stability of that compound. Some metal hydrides are so tbermally unstable that they decompose so rapidly that the fluorocarbon metal compounds cannot be prepared in high yield. Therefore, we prefer to use those metal hydrides which are stable under the conditions of the reaction employed in our hydrometallation process. Tberef-ore, the inost preferred metal hydride applicable in our process is manganese pentacarbonyl hydride. Our process can be performed with or without the -1,290,343 4 presence of a solvent. N"en a solvent is used, an unreactive hydrocarbon solvent is preferred. An illustrative but not limiting list of these hydrocarbon solvents is npentane, n-hexane, isooctane, and petroleum ether. .5 Our process can be @conducted at a temperature within the range of 15' to 80o C. A preferred temperature range is 20' to 65' C. Temperatures higher than 80' C. cause extensive decomposition and undesirable side reactions which reduce the yield of the desired product. Tempera10 tures lower than 15' C. unduly prolong the reaction time. Our process is applicable when pressures within the range of 0.3 to 10 atmospheres are employed. A preferred pressure range is from 5 to 8 atmospheres. Higher pressures can cause violent decomposition of the unsatu15 rated fluorinated hydrocarbons. Lower pressures unduly prolong the reaction time. The reaction time used in our process is not a trlity independent variable. If a relatively low temperature and pressure are emp yed, e reaction time wi exten 20 If a high temperature and pressure are used, the reaction time will be correspondingly diminished. We prefer to employ reaction conditions in which the reaction time falls within the range of ton hours to seven days. A inost preferred reaction -time is 20 hours to six days. 25 A-itation of the liquid mixture is preferred since a smoo@ther reaction rate is accomplished. However, -a@itation is no-t essential. The a-.itation may be effected' by either stirring the reaction mixture or rocking the reaction vessel. 30 Our products are readily separable from the reaction mixture by those standard techniqiaes used in the chemical prior art. LiqLiid products can be removed by distillation or extraction. Solid products can be removed from the Teaction rnixture by fractional crystahization -or subliina35 tion. Both liquid and solid products can be separated by chrornatographic techniques. Generally, our products are low melting solids. We prefer to remove them from the reaction mixture by sublimation of the solid residue remaining after the solvent has been removed by dis40 tillation. Our process is illustrated by the following examples. The amounts of reactants and solvents are given in parts by weight per 100 parts by weight and the yields are expressed in percent by wei-,ht of the theoretical yield, cal45 culated @on the basis of the amount of metal hydride employed, unless otherwise indicated. EXAMPLE I 1,1,2,2-teti-aflitot-oethyl manganese pentacai-bonyl 50 A mixture of manganese pentacarbonyl hydride, 12.5 parts, tetrafluoroethylene, 12.5 parts, and n-pentane, 75 parts, were charged into a suitable stainless steel pressure vessel equipped with heating means, temperature means, 55 pressure means, stirring means, iand gas inlet and outlet ports. The temperature was maintained at 25' C. and a pressure of 5 atmospheres was initially impressed upon the mixture. The mixture was stirred throughout the reaction 60 pei-iod. After 22 hours the vessel was vented to the hood and then,opened. The liquid contents were decanted into a suitable distillation vessel. The pressure vessel was washed with n-pentane until the washings were colorless, and these washings were 65 combined with the liquid reaction mixture. The mixture was then distilled at room temperature and at reduced pressure (20 mm.). The solid residue was transferred to a suitable sublirning apparatus and sublimed at room tomperaturre and at 0.1 70 mm. pressure. The product, 1,1,2,2-tetrafluoroethyl manganese pentacarbonyl, was the most volatile component and was the fi@rst fraction dep@osited on the collection surface. The product, a pale yehow solid, M.P. 30.5- 31.5' C., was obtained in yield of 69 percent. An 75 analytical sample was further purified by resublimation.
[3]Calcul,,Lted for C71IF405Mn: C, 29.4; 1-1, 0.34; F, 25.6; Mn, 18.6. Found: C, 28.3; H, 0.41; F, 25.38; Mn, 18.91. The molecular weight, determined isoplestically, wias 297 grams/mole. The product was further characterized by infrared sp,-ctrophot6metry. Strong p--aks occurred at 5 4.91, 4.96, 5.07, 7.39, 9.14, 9.88 and 10.09 m;crons when the sample was run in CS2 and NaCl optics. Nuclear magnetic resc-narce, 19F, studies demonstrated two peaks, one at 59.8 p.p.m. and the @other at 122.8 p.p.m. O@n treatment with bromine, tetrafluorobromoethane and car10 bon monoxide were obtained in quantitat-@Ve y-ield. EXAMPLE 11 1,1,2,2-tetrafliioi-oethyl inangaiiese pei?taccii-boityl Ma,,igai,ese pentacarbonyl hydrid@-, 43.5 parts, and tetra15 fli-loroethylene, 56.5 parts, were added to a previously evacuated Pyrex bulb and tli@- bulb was then sealed. 'L he pressure inside tlie bulb when the te.,nperature was 25' C. was 0.6 atmosphere. After 24 hours at 25' C, the bulb was opered caret'ully, and tle liq-aid mixture decanted 20 into a suit-,ible distillation vessel. Tiae bulb was washed with n-pentane until the washi-iigs were colorless. Isolation of the product by the procedure use-d ii Example 1 yielded the same prodtict as above, 1,1,2,2-tetrafluoroelbyl man.-apese pentacarbonyl, in 45 percent yield. 25 EXAMPLE III 1,2,2-triflucro-l-chloroethyl manganese pentacai-botz3,1 The procedure of Exanipl-, I was repeated us,'@n-, man30 ganese 1)entacarbonyl hydride, 21 parts, ti-iiluorochloroethylene, 11 parts, and n-pentane, 68 parts. A p-,Ie yetlow solid, HCFCI-CF2Mn(CO)5, 1,2 ,2-trifliioro-l-chloroethyl manganese pentacarbonyl, M.P. 43-44' C., Ni,as obtained in 40 percent yield. The moleci ,Iar we;,-ht, d-,termined isopiestically, was 382 -rams per mole. The in35 fraied @pectrum,'with CS2 a-id NaCl oi)ti, -s as the solvent, contained strong peaks at 4.92, 4.98, 5.07, 7.46, 7.62, 8.00, 8.81, 9.25, 9.47, 9.98, 10.38 and 14.36 microns. EXAMPLEIV 4 0 1,2,2-triflito7-o-l-chloi-oethyl t?zan,-aiiese petitacai@boizyl The procedure of Example I was redeated using mangaqese i)eil@agarbonyl hydride, 4 pa@-ts, 1,1,2-trift-doro-2- chloroethyiene, 17.5 parts, and tetrahydrofuran, 78.5 45 parts. The temderature was 25' C., the initial pressure was 6.7 atmospf@eres and the reaction time was 28 hours. Th@- prodtict, 1,2,2-triquoro-l-chloroethyl manganes-, pentacarbonyl, identical to the prodtict formed in Example 111, wis obtained in 22 percent yield. 50 EXAMPLE V 1,1,1,4,4,4-hexafli,toi-o--?-bittenyl i7ia@,.,aiese pe7itacari)o!?Yl The procedure of Examt)le I was repeate d usin.- maigar@ese pentacarbonyl hydride, 15.5 parts, 1, 1, 1,4,4,4-hexa- 55 fluorobutyne-2,15.5 parts, and n-pentane, 69 parts. The reactioti temoerature employed was 25' C. The initial pre,,sure was- 4 atmospheres a@id, ti-,e react-on time was five days. A pale ye'low liou-!d, T%I.P. around C,. C., 1,1,1,4,4 60 14-hexa@quoi7o-2-btitenyt - pentacai@oonyl was prepared in 12.5 pereant yield. @he product was exclusively composed of the trans isomer. The infrared spectrum obtained usi@qg tetrachloroethylen@.- as the solvent ar-d NaCl optics contaiiied strong peiks at 4.72, 4.94, 4.99, 5.08, 6.19, 6.22, 7.81, and 8.9 microns. 65 EXAMPLE VI 1,1-d,;chloro-2,2-dij?ttoroethyl 1?iaizgaiiese peiitacai-boi?yl The procedure of Example I was repeated usin.- man- 70 ganese pentacarbonyl hydride, 4.0 parts, - 1,1-@dicbloro-2,2- d;fluo@-octhylene, 19 parts, and n-pentarle, 71.5 parts. The reaction te.,mperatu-re was 25' C., the i-i:tial p@-essure was 5.5 atmospheres ard the reaction tiyre was 48 hoirs. A yellow sojid, M.P. 6-0-70- C., 1,1-di chi@oro-2,2-di.,ILioro- 75 6 ethyl man@-anese pentacarbonyl, was obtai.-ed in 39 percent yield. Calculated for C7HO5F2Cl2Mn: C, 25.5; H, 0.30; F, I i.5; Mn, 16.3. Found: C, 25.77; H, 0.38, F, 10.1; Mn, 1.6.3. The iiifrared spectrum obtaiped in the same manner as the speclrum described in Exampl,- I had stron- peaks at 4.93, 4.99, 5.07, 8.13, 10.29 and 12.36 micro-@i's. EXAMPLE VII 1,1,2,2-teti-aflitoi@oetlivl nzo@l,bdeizitiii (c),clopeitiadieizyi) ti-ica)-holly! T@i-. procedure of Example I was repeated usin.- cyclopentadienyl molybdenum tricarbonyl hydride, 10.5 parts, tetrafluoroethylene, 10.5 parts, and n-pentane, 79 parts. The r,@action temperature was 25' C., the initial pressure was 4 atmospheres, and the reaction time vas 16 hours. Alter sublimation at 65' and 0.1 mi-n. pressure a yellow orange solid, meltin,@ point 54' C., 1,1,'@, 2-tetrafluoroethyl molybdenum(cyclopentadienyl)tricarbonyl, was obtained in 11 percent yield. Calculated for ClOH603F4Mo: C, 34.7; H, 1.7; F, 22.0; Mo, 27.7. Found: C, 34.94; H, 1.73; F, 21.91; Mo, 27-48. The melting point, deterniined isopiestically, was 341 grams per mble. The infrared spectrum obtained in the same manner as the spectrum described in Example I contained stron- peaks at 4.90, 5.00, 5.14, 7.38, 8,54, 8.60, 9.11, 9.93, 10.27, 10.90, 12.17 and 12.91 microns. EXAMPLE VIII 1,2,2-triflitoi-o-l-chloi-oethyl iiiolybdeizuiii (cyclopeiiiadieiz3,I) ii-icarboiiyl The procedure in Example I was repeated usin- cyclc)penlad:enyl molybdenum tricarbonyl hydride, 21 parts, trifluoro ciloroetfiylene, 31 parts, and n-pentane, 48 parts. The temperature of the reaction mixture ,@,as niaintained at 25' C. The initial pressure was 7 atmospheres and tne reaction time was three days. The product, an oran-e solid melting at 36.5 to 38' C. was 1,2,2-trifluoro -l-chl'oroethyl molybdenum(cyclop@- ntadienyl)tricarbonyl. it was isolated by sublimation at 65' C. and 0.1 mm. This product was @obtained in 4.3 percent yip-@ld. The compound is son-iewhat unstab'ie at room teniperature and decomposes slowly (arproximately 20 percent per day). The infrai-ed spectru-m obtaii-led under the sanie conditioiis as the spectrum dese.,ibed in Exatuple I contained strong peaks at 4.87, 5.08, 7.43, 8.72, 9.17, 9.39, 10.45, 12.14, 12.88 and 13- 25 microns. The peak occurrin@ at 5.08 microns was broad and could possibly have been'resolved to two or more cc)rnponents. EXAMPLEIX 1,1,2,2-teti-t7flItoi,oeth371 tUll,@Stell (cyclopeiztadiefzyl) ti-icartoi@,yl '.he proc@dure of Example I was repeated usin- cyclopeitadienyl tunfsten tricarboiyl hydride, 15 parts', tetraftuoroetliy@lene, 24 parls, and n-pentan,-, 61 -parts. The r-action temperature was 60' C., the original pressure was 8 atmospheres and the time of the rea-@tion was 28 houxs. Ti@e product c)btaiiied by subl;mation at 65' C. and 0.1 nim. i)ressure was a yellow orange solid, melting point - 50-51' C., and was identified as 1,1,2,2-tetraf'iuoroethyl t,,ingsten (cyclopentadienyl N, tr;Carbonyl. EXAMPLE X Bis(1,2,2-ti-ifl@loi-o-l-chloi-oetlzill)ii-oil teti-acai-botzyl The proecdlre iii Example I is repeated Lis-ng iron carboiiyl dihydride, 18 parts, difluoro cliloroethylene, 25 parts, and n-pentane, 57 parts. The reaction temperature is 125' C., the initial pressure is 6 atmospheres and the tim-. of the reaction is 24 hours. The product, bis(1,2,2trifluoro-l-chloroetiayj)iron letrac-irbonvi :s a pale yellow. The iifrared spectruni obtained under' the same conditions as the spec,@rum obtained in Example V contains strong bands at 4,64, 4.78, 7.43, 8.53, 9.13 aiid 10.22- m;crc)ns,
[4]7 Other fluorocarbon transition metal compounds can be prepared according to the conditions enumerated in the following table. -,290,343 exhibits a gain '@n wei,@ht of about 0.02 gram. The cloth has greatly decreased resistivity and each individual fiber proves to be a conductor. An applicatiorl of current to TABLEI Tem- Iriitial Metal Hydride Fluorocarbon Solvent Product per,,iPres- Time ture sure (CSH5)2Tal-13 --------------------------- CF2=CF2 --------- n-Pentane-- (I-ICF2-CF2)3Ta(05H5)2 --------------------- 25' 6 6 days. Tert.butyl Cr(C 0)3H ------- CF2=Cr@ 2--------- n-Hexane-- HCFz-CF2- Cr(tert-butylC5H4)(CO)3 ----- 15, 10 7 days. (CO)3- . 25' 4 6 days. C113 Mo (C 0) 3H -------------- CF2=CFCI ------- Petroleum HCFCI-CFz-Nlo CH3) ether. (C 5T-15) 2MC)lf2 --------------------------- CF2@CFC12------ n-Pentane-- (C5H5)2MO(CF2-C C12)2 -------------------- 251 6 24 lirs. CF3H (C5Hs)2W H2 --------------------------- CFr--C@-CCF3- Isooetane-- (c5H5)2w(u@u-CF3)2 --------------- ------ 25' 6 65 lirs. 0 Ho I C4H W(CO)3H --------- CF2=CF2 --------- n-Pentane-- HCF2-CF2-R' (C 0)3H25' 7 24 tirs. HRe(CO)5 ----------------------------- CF2--CF2 --------- ----- do ------ HCF2-CF2- Re(CO)s ----------------------- 60' 0. 3 28 hrs. (C6H5)2ReH ---------------------------- CF2=CF2 --------- ----- do ------ HCF2-CF2- Re(C5II5)2 --------------------- 25' b 24 hrs. CH3 I C5H4-Fe(C 0)2H ---------------------- C F2=0 012 ---- --- n-Hexane-- HO C12-CF2-Fe(Ol-13@c5H4) (C 0)2 -------- 25' 8 10 lirs. H2RU(C 0)4 - --------------------------- CF2=CF01 ------- n-Pentane-- (CHFCI-CF2)2RII(C 0)4 ------------------- 2,51 8 28 brs. H20s(C 0) 4 ----------------------------- OF2=CF2 --------- ----- do ------ (HCF2-C F2)2-OS(C 0)4 ------------------ -- 60' 7 24 lii,s. HCo(00)4 ------------------------- --- C F2-- C F2 --------- ----- do ------ - T.I 0 F2- C Fz-- C o- (C 0) i --------------------- 80, 0.3 26 lirs. HRh(CO)4 ----------------------------- CF2@CF2 --------- ----- do ------ HCF2-CF2-Rli-(C 0) I ------------------ -- 25' 4 28 hrs. HIr (C 0) 4 ------------------------------ CF2=CFCI ------- ----- do ------ H C P c 1- C F@--li. (c 0) .1 -- ----------------- 2@,l 3 27 lirs. L(C2fI5)3P]2Pd(I-1) Cl ------------------- CF2=CF2 --------- ----- do ----- - HCF2--CF2-Pd(Cl)[P(C2H5)31 ---- ----- 25. 6 28 I)rs. [(<:7>),P]Pt(H)CI --------- CF2=CF2 --------- ----- do ------ HOF2-CF2Pt(Ol) [P(<7>),] ------ 25- 6 25 hr,. Nuclear magnetic resonance spectrophotometry demonstrates that in aR the compotinds produced by our process, 40 a CF2 is adjacent to the metal atom. This phenomena is exhibited when unsymmetrical fluorinated hydrocarbons are used in our process. Our new compounds are useflil antiknocks when added to patroleum hydrocarbons. Further, they may be used as 45 supplemental antiknocks in addition to a lead antiknock already present in the fuel. Typical lead antiknocks are the lead alkyls such as tetraethyeead, tetrabutyllead, tetramethyread and various mixed alkyls such as - dimethyldiethyllead, diethyldibutyllead and the like. When used as 50 a supplemental antiknock, our compounds also act as a scavenger in combination with typical halogen scavengers such as ethylene dichloride, ethylene dibromide and tlic like. Our novel compounds are not only useful intermediates 55 as shown above but are flirther useful in their own right in metal plating applications. In order to effect meta plating with our novel compounds, they are decomposed in an evacuated space containing the object to be plated. On decomposition, they lay down a film of metal on the 60 object contained within the enclosure. The gaseous plating may be carried out in the presence of an inert gas so .as to prevent oxidation of the metal during the plating toperation. The gaseous plating technique described above finds 65 wide application in forming coatings which are not only @decorative but also protect the underlying substrate material. Since molybdenum is a conductor, this technique enables the preparation of printed circuits which find wide application in the electrical arts. Deposition of metal on a glass cloth illustrates the ap- 70 plied processes. A glass cloth band weighing one gram is dried for one hour in an oven at 150' C. and dipped in one of our compounds. The tube is heated at 400' C. for one hour after which time the tube is cooled and oppreo. Ti@e, cloth has a metallic grey appearance and 75 the cloth causes an increase in its temperature. Thus, a conduoting cloth is prepared. This cloth can be used to redtice static electricity, for decoration, for thermal insulation by reflection and as a beating element. Our new compounds also find utility as additives for Itibricant oils, and greases to increase their antiwear activity. They are also used to control the rate of combustion of pyrophoric materials such as solid rocket propellants. Our compounds are also biocidally active and find utility as fungicides, herbicides, pesticides and the like. Our compounds are also utilizable as monomers in the preparation of polyrnericmaterials. Having fully descri-bed our novel compounds, their novel mode of preparation, and their manifold utilities, we desire to be limited only within the scope of the apper@ded claims. We
