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United States Patent 0 Patented June 7, 1966

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United States Patent 0 Patented June 7, 1966 3,254,953 United States Patent 0 Patented June 7, 1966 2 in which Et. is a tridentate non-cyclic ether. These 3,254,953 compounds have high stability and also the tridentate ORGANOMETALLIC COMPOUNDS ether, Et. is relatively non-volatile (having a vapor pres Robert P. M. Werner, Farmington, Mich, assignor to sure of not more than one-tenth that of vanadium hexa Ethyl Corporation, New York, N.Y., a corporation of Virginia carbonyl). Typical tridentate non-cyclic ethers which No Drawing. ?riginal application Apr. 10, 1961, Ser. ful?ll the requirements of Et. are diethyleneglycol di No. 101,652. Divided and this application May 13, methylether, diethyleneglycol dibutylether, dipropylene 1964, Ser. No. 374,223 glycol dimethylether, dipropyleneglycol dibutylether, di 1 Claim. (Cl. 23-203) ethyleneglycol methylethylether, and the like. A pre 10 ferred tridentate ether is diethyleneglycol dimethylether. This application is a division of my application Serial In the preferred form of my process in which the acid No. 101,652, ?led April 10, 1961, now abandoned, which is a non-volatile one, as described above, and the ether in turn is a continuation-in-part of my application Serial present in the hexacarbonyl vanadate-containing salt is No. 83,870, ?led Jan. 23, 1961, now abandoned. non-volatile, I can separate the vanadium hexacarbonyl This invention relates to processes for forming vana product very readily from the system by heating under dium hexacarbonyl. More speci?cally, the invention re reduced pressure. Since both the acid reactant and the lates to processes for forming vanadium hexacarbonyl ether which is liberated during the reaction are relatively by treatment of an alkali or alkaline earth metal-ether non-volatile, they are not vaporized during this heating ate salt containing the hexacarbonyl vanadate anion. step. Thus, the vanadium hexacarbonyl product is sub An object of this invention is to provide novel proc limed off in a highly pure state, uncontaminated by either esses for preparing vanadium hexacarbonyl. A further ether or acid. object is to provide processes for preparing vanadium A preferred non-volatile acid which I employ in‘ my hexacarbonyl which utilize as the starting material an process is phosphoric acid. This acid is strong, non alkali or alkaline earth metal-ethenate salt containing the oxi-dizing, and extremely non-volatile. Its use in my hexacarbonyl vanadate anion. Additional objects will 25 process makes possible the obtaining of very high yields become apparent from the following discussion and of vanadium hexacarbonyl by simply subliming the vana claim. ' - dium hexacarbonyl from the reaction mass at normal The objects of my invention are accomplished by pro temperatures under reduced pressures. viding several processes for converting an alkali or alka To further illustrate my process, there are presented line earth metal-etherate salt containing the hexacarbonyl the following examples in which all parts and percentages vanadate anion to vanadium hexacarbonyl. The alkali are by weight unless otherwise indicated. metals are lithium, sodium, potassium, rubidium, and Example‘ I cesium. Appropriate alkaline earth metals are calcium, ‘ strontium, barium, and magnesium. Other appropriate A mixture comprising 3.325 grams of sodium bis(di metals are aluminum and zinc. The ?rst and preferred ethyleneglycol dimethylether) hexacarbonyl vanadate in process for accomplishing this end involves treating an 25 ml. of para?in oil was degassed in vacuum and 9 .alkali or alkaline earth metal-ether-hexacarbonyl vana m1. of 85 percent phosphoric acid were added. The date salt with a strong non-oxidizing acid. A large ex ?ask in which the reactants were contained was attached cess of acid, generally from about 10 to about 100 times > to a vacuum pump which was connected in series with the stoichiometric amount, is employed in this reaction. a Dry Ice trap. During the course of the reaction, vapors The reaction is carried out under normal temperature were continuously pulled from the reaction mixture and conditions which are generally in the order of room passed through the cold trap. After gas evolution ceased, temperature or about 25 ° C. In order to avoid decom the blue solid ‘formed in the reaction mixture was re position of the vanadium hexacarbonyl product, the re moved and puri?ed by flash sublimation through a cal action is preferably carried out under an inert atmos cium cloride-containing tube into a Dry Ice cooled trap. phere such as nitrogen, .argon, krypton and the like, at After several resublimations under full pump vacu-um, about atmospheric pressure or under vacuum. In order there was obtained the analytical sample. The freshly to assure an even reaction rate the reaction mixture is sublimed vanadium hexacarbonyl is volatile and is solu preferably agitated. ble in hydrocarbons and ether. Its structure was con The vanadium hexacarbonyl product can be readily ?rmed by means of its analysis and the infrared spectrum separated from the reaction mixture by conventional of the compound. means since the product is hydrophobic and floats on the surface of the reaction mixture. One simple means of Example 11 separation is to ?lter off the vanadium hexacarbonyl To a reaction vessel which was connected with a vacu from the reaction mixture. 55 um source in series with a cold trap was added 7.8 grams In a preferred version of my above described process, of sodium bis(diethyleneglycol dimethylether) hexacar a strong non-oxidizing acid is employed as the acid re bonyl vanadate. After evacuating the vessel to a pres actant, which acid is relatively non-volatile and has a sure of 0.1 mm. of mercury, 40 ml. of 100 percent phos vapor pressure in the order of not more than one-tenth phoric acid was added. Very little gas evolution occurred that of vanadium hexacarbonyl. When utilizing the non 60 and hydrophobic, dark vanadium hexacarbonyl formed volatile acid as the reactant, the ether present in the on the top of the liquid surface. The vanadium hexa vanadium-containing salt is a relatively non-volatile one carbonyl was sublimed from the ‘reaction vessel through I having a vapor pressure which is much less than that of a calcium chloride-containing tube into a cold trap vanadium hexacarbonyl. This assures that during the (through straight tubing free from constrictions) by heat separation step, the vanadium hexacarbonyl product will 65 ing the reaction vessel at a temperature of 50 to 550° C. not be contaminated by the ether which was present in the alkali or alkaline earth metaléether-hexacarbonyl under the partial vacuum in the system. After less than vanadate starting material. Preferred hexacarbonyl van two hours of heating, the vanadium hexacarbonyl prod adate~containing salts which I employ in my process have uct had condensed quantitively in the Dry Ice trap form the formula: 70 ing large crystals and leaving a colorless and vanadium free phosphoric acid behind in the reaction vessel. The yield of product was 3.3 grams of crystalline vanadium 3,254,953 3 4 carbonyl which corresponds to a yield of 98 percent of addition of the tropenium bromide to the sodium bis(di the theoretical. 1 ethyleneglycol dimethylether) hexacarbonyl vanadate, a Example 111 reaction occurred and there is formed a bluish precipitate of vanadium hexacarbonyl. In addition, gas is evolved. An aqueous solution containing 0.10 mole of a sodium The bluish solid dissolved in the supernatant layer of n dimethoxyethane-hexacarbonyl vanadate salt is placed in heptane giving a yellow color. The vanadium hexacar a reaction vessel under a nitrogen atmosphere. There bonyl is isolated by ?rst stripping off the solvent followed are then added 3 moles of hydrochloric acid in aqueous by sublimation of vanadium hexacarbonyl from the resi solution over a 10-minute period with stirring of the re due which also contains l-cycloheptatrienyl cyclohepta action mixture and external cooling of the reaction vessel. 10 triene. The reaction mixture is then ?ltered to remove the hy ' ' Example VII drophobic vanadium hexacarbonyl product. The prod uct is washed with water and sublimed over calcium chlo A clear yellow solution, obtained by mixing an aqueous ride to give a good yield of vanadium hexacarbonyl. solution of two grams of sodium bis_(diethyleneglycol dimethylether hexacarbonyl vanadate with an aqueous Example IV solution containing 7.8 grams of ammonium chloride fol To a reaction vessel containing an aqueous solution of lowed by ?ltration, was treated with 2.5 grams of mer 0.2 mole of a potassium-dimethoxyethane hexacarbonyl curic chloride dissolved in water. There was produced vanadate salt under nitrogen are added a mixture compris— an orange-pink, non-crystalline precipitate, the mercuric ing 0.6 mole of trichloroacetic acid in 3 moles of ethyl 20 salt of hexacarbonyl vanadate, which was ?ltered under hexanoic acid. The addition of the acid takes approxi nitrogen, washed with water and dried in vacuum. Dur mately 10 minutes with stirring of the reaction mixture. ing the drying operation, it was observed that bluish ma The reaction mixture is then discharged and poured over terial was collecting in the cold trap which was connected ice to yield a precipitate which is removed by ?ltration. in series with the vessel containing the material being The precipitate is then washed with water, ?ltered and 25 dried. This material was analyzed and found to be van dried over calcium chloride to give a good yield of vana adium hexacarbonyl. dium hexacarbonyl. Similar results to those set forth in Examples VI and ' ' Example V VII are obtained when I employ other oxidizing agents such; as ferric chloride, stannic chloride and the like. To an evacuated reaction vessel is charged 0.1 mole of 30 Thus, vanadium hexacarbonyl is obtained from oxidation sodium bis(dipropyleneglycol dimethylether) hexacar of ‘a potassium-dimethoxyethane-hexacarbonyl vanadate bonyl vanadate.
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