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Definitions

• the complexing agent preferably comprises a compound of a transition metal of Group IVb, VIb or VIII, e.g. an acetylacetonate, organic acid salt or alkanolate of titanium, chromium, iron, cobalt or nickel. Quaternary ammonium or alkali metal salts may be used as conductors.
• a transition metal of Group IVb, VIb or VIII e.g. an acetylacetonate, organic acid salt or alkanolate of titanium, chromium, iron, cobalt or nickel.
• Quaternary ammonium or alkali metal salts may be used as conductors.
• the products are suited for catalysis of hydrogenation, oligomerization and isomerization.
• the present invention relates to the electrochemical production of organometallic complexes of transition 5 metals, free of carbon monoxid
• Organometallic compounds are by definition those compounds in which the metal is bound to a C atom or to a C-C multiple bond either through a 8 bond or through a 1r bond (see, for example, 1.1. Eisch, The 10 Chemistry of Organometallic Compounds," The Macmillan Company, New York, 1967, p.l).
• metals are of great technical interest since in many cases they are active catalysts for the hydrogenation of unsaturated organic compounds, for the oligomerization of 1,3-diolefins, for the codimerization of olefins or alkynes with l,3-diolefins (cf. G. Wilkeandcollaborators, Liebigs Ann. Chem. 727, 143-207 (1969) or,
• transition metal complex compounds can be preparedbythe reduction of transition metal compounds by means of metal alkyl, cycloalkyl, aryl oraralkyl: compounds ofi Groups I to ill metals in the presence of organic complexing compounds.
• Electronv donors whichcontain C-C multiple bonds or atom groupings with non bonding electron'pairs are the complex-ing agents, ex-
• transition metalslused accordingzto the invention do not react with the complexingagents of them-- vention when they arein elemental form,- e.g.', in the reduced at the cathode to the zero valence state and,
• the zero-valence metal combines with other atoms to form a crystal lattice and hence larger aggregates, reacts with the complexing agent present in the electrolyte to form the organometallic complex.
• thiseme ansthatthe organometallic compound must a] ready be present'and the metal then is reduced from a higher to a lowervalence.
• MnCpz as the case may be) --m formiin'which-it: is bound toanauxiliary metal, as alkali metal 'cy'clopentadienyhfor example, and all that the electrolysis does isbring-about a transmetallization of the radicalz 'Th'e same isthe case even when, according to a variant process described in U. S. Pat. No. 2,960,450, the alkali metal cyclopentadienyl compound is constantly being formed in the electrolysis cell by the reaction of the cathodically separated alkali metal with cyclopentadiene.
• transition metal compounds of higher valence state are reduced in the presence of compounds which do not function as complexing agents in relation to the metal in this valence state. Nevertheless, the cathodic separation of metal does not takeplace, and the complex compounds formed with the metal are obtained in the lower or zero valence state in good yields. This establishes that the organometallic compound is first formed by the reaction of the invention.
• the reaction of the invention can also be used for the preparation of zerovalence or low-valence coordination compounds of the transition metals with alkyl, aryl, alkyloxy or aryloxy compounds of trivalent phosphorus, arsenic or antimony.
• These are electron donors which have a nonbinding pair of electrons.
• An example is the preparation of tetrakis-[triphenylphosphine]-nickel() Ni[C H from a bivalent nickel compound which is not complexed with triphenylphosphine.
• transition metal compounds of the fourth to seventh sub-group and of the eighth group of the Periodic System (lVb, Vb, Vlb, Vllb, Vlll) are used as transition metal compounds, examples being titanium, zirconium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, palladium and platinum, preferably the metals ofGroup VllI, Vlb and Nb, especially nickel, cobalt, iron, chromium and titanium.
• the electrolysis those compounds of the transition metals which are soluble in the solvents used.
• Such compounds are the metal acetylacetonates, salts of organic acids or salts with other organic radicals, e.g., alkanolate radicals or complex alkanolate radicals such as [Al(OC H Often the an hydrous halides of the transition metals can be used, either by themselves or in the form of complex compounds with Lewis bases, e.g., TiCl TiCl '3 THF, FeCl or CrCl 3 THF (THF tetrahydrofurane).
• Lewis bases e.g., TiCl TiCl '3 THF, FeCl or CrCl 3 THF (THF tetrahydrofurane).
• the complexing agents for the coordination compounds to be prepared according to the invention are electron donors containing CC multiple bonds or atom groups with non-bonding electron pairs.
• the following are especially suitable:
• Cyclic polyolefins such as cyclooctadiene-(1,5), cyclooctatetranene, cyclododecatriene-( 1,5,9); cyclic monoolefins with strained double bonds or l,3-diolefins or alkynes.
• the alkyl and aryl compounds of elements of Group Va of the Periodic System with an atomic number of at least 15, examples being tertiary phosphines, arsines, stibines and phosphites.
• Suitable solvents are aromatic hydrocarbons such as benzene and toluene; aliphatic or cycloaliphatic monovalent or polyvalent ethers such as diethyl ether, tetrahydrofurane, dimethoxyethane or 2,2-dimethoxydiethylether or other dialkyl ethers of ethylene glycol or of dior triethylene glycol; cyclic l,2-propylene carbonate; and especially pyridine, have proven desirable for the process of the invention.
• the transition metal compounds have extremely little if any conductivity in the preferred solvents, it is advantageous to add difficultly reducible salts which dissociate into ions to serve as conductors, especially tetraalkylammonium halides or ammonium compounds with other acids as well as lithium halides.
• the cathodes can be made of any metals that are inert with respect to the electrolyte, e.g., Al, Hg, Pb, Sn, graphite, iron, platinum, nickel, titanium, etc.
• anodes those metals whose complex compounds are to be prepared; in this manner the preparation of the organometallic complex compound from the metal (used as the anode) and the complexing agent can be performed by electrochemical methods as an overall reaction for the electrolysis process. The metal then dissolves in proportion to the current applied. In many cases the use of an aluminum anode has proven especially desirable.
• the preparation of the transition metal complex compounds is performed in the following manner: solutions or suspensions of compounds of the transition metals in an appropriate solvent, with the addition of a conducting salt if necessary, are electrolyzed between two metal electrodes which are best located at a very short distance from one another of about 0.2 to 5 cm, at temperatures between -40 and +lOOC, preferably 20 and +50C. After the calculated amount of current has flowed through the cell, the complex com-- pound can be isolated from the reaction mixture. If the resulting transition metal complex compounds are to be used as catalysts, however, the catalytic reaction can be performed in the electrolysis cell itself during the electrolysis by the addition of the components that are to be transformed by the catalyst.
• transition metal complex compounds can be prepared by the process of the invention:
• cyclooctatetraenetitanium chloride [CsHsTlCilg from titanium tetrachloride ariazyldbcia'tetiieaea all-trans-cyclododecatriene-( 1 ,5,9 )-nickel(0)-triphenylphosphine(C l-l, )Ni'P(C,l-l from nickel acetylacetonate, cyclododecatriene-(1,5,9) and triphenylphosphine;
• Cobalt-containing catalyst solutions by the electrolysis of cobalt acetylacetonate or cobalt-bis-[tetraethoxyaluminum] in THF. This solution can transform butadiene to 5-methylheptatriene or transform diphenylacetylene to hexaphenylbenzene.
• catalyst solutions containing nickel which transform butadiene to cyclododecatriene- (l,5,9) or to cyclooctadiene and vinylcyclohexene.
• catalyst solutions are formed which transform butene-(Z) to hexamethylbenzene.
• the CO-free organometallic complex compounds of transition metals obtained by the process of the invention, or their solutions, can be used as catalysts for the oligomerization of olefins and diolefins.
• EXAMPLE 1 A solution of 12 g 45.6 mmoles of nickel (ll) acetyl acetonate and 5 g of tetrabutylammonium bromide in 100 ml of THF is saturated with butadiene and electrolyzed at about 20C between two aluminum electrodes each having an effective electrode surface of 20 cm and spaced 3 cm apart. Current: 30 mA, 60 V. After the passage of 46.5 m faradays, butadiene is introduced into the electrolysis cell at 20C. After the passage of a total of 100 m faradays the solution is vacuumdistilled, finally at 60Cand 0.001 mm Hg, passing all volatile substances into a chilled condenser. 1n the fractionation that followed, there was obtained 21.5 g of a mixture of the following cyclododecatriene-( 1,5,9) isomers, boiling at 100 to ll0/l5 mm Hg:
• EXAMPLE 2 A solution of 7.0 g (27.3 mmoles) of nickel (ll) acetylacetonate, 28.6 g (109 mmoles) of triphenylphosphine and 2 g of tetrabutylammonium bromide in 50 ml of THF is electrolyzed at 40C between two aluminum electrodes. Current: 60 V, 40 mA, at 3 cm electrode spacing; amount of current applied: 55 m faradays. A dark brown solution results, from which reddish brown, glittering crystals precipitate. After filtering, washing with absolute methanol and drying, 25 g of nickel tetrakistriphenylphosphine is obtained. Yield: 83% of theory.
• EXAMPLE 3 Twelve g (46.5 mmoles) of nickel (ll) acetylacetonate and 2.5 g of tetrabutylammonium bromide are dissolved in 100 g of pyridine. After the addition of g (92.5 mmoles) of cyclooctadiene-( 1,5) the solution was electrolyzed at 0 C between two aluminum electrodes. Current: 30 mA, 20 cm per electrode surface; 18 volts. During the electrolysis the color of the electrolyte changes from blue green to brownish yellow.
• Weight loss of the aluminum anode 0.72 g, corresponding to 100% of theory.
• the electrolyte After the addition of a fresh quantity of nickel acetylacetonate the electrolyte can be used for another electrolysis.
• EXAMPLE 4 10.2 g (40 mmoles) of nickel (ll) acetylacetonate, 3 g of tetrabutylammonium bromide and 16 g (154 mmoles) of cyclooctatetraene are dissolved in 1 16 g of pyridine and electrolyzed at 20C between two aluminum electrodes. The electrolyte changes color from blue to dark red. After about 20% of the required amount of current has passed, darkly glittering crystals of cyclooctatetraene-nickel precipitate. After a total of 1,770 mA.h, the crystals are filtered at 20C and washed with benzene. Yield: 3.4 g, corresponding to 63% of theory. After concentration of the mother liquor, another 1.7 g can be isolated. Total yield: 5.1 g, corresponding to 93% of theory.
• EXAMPLE 5 Ten g (39 mmoles) of cobalt (ID-acetylacetonate and 6 g of tetrabutylammonium bromide are dissolved in 100 ml of THF. After saturating the solution with butadiene, it is electrolyzed between two aluminum electrodes with 50 to 30 mA and 25 volts. After m faradays have been passed, the solution is freed of the THF in vacuo at 0.02 mm Hg. The residue is dissolved in benzene. This catalyst solution transforms butadiene at 20C into 5-methylheptatriene-( 1,3,6) and noctatriene.
• Butadiene is introduced into a solution of 4.7 g (10 mmoles) of Co[Al(OC H and 5 g of tetrabutylammonium bromide in 60 ml of dimethoxyethane during the electrolysis. After the passage of 535 mA.h, the catalyst solution is fractionally distilled, yielding 22 g of 5 -methylheptatriene-( 1,3,6).
• EXAMPLE 7 6.3 (33 mmoles) of titanium (IV) chloride and 6.9 g (67.5 mmoles) of cyclooctatetraene are dissolved in 70 ml of THF and electrolyzed at 40C between two titanium electrodes. Current: 10 mA, 60 volts. A dark solution develops, out of which dark green crystals precipitate. Amount of [C H TiCl] 6.3 g( 17 mmoles) of the dimeric compound. Molecular weight determined by mass spectrometry: 374.
• EXAMPLE 8 A solution of 10.4 g (40.4 mmoles) of nickel (ll) acetylacetonate and 1.9 g of tetrabutylammonium bromide in ml of pyridine is electrolyzed between two aluminum electrodes after the electrolytes have first been saturated at 20C and then kept constantly saturated by a moderate infeed of butadiene during the electrolysis.
• EXAMPLE 9 The procedure is the same as in Example 8, but 80 The liquid reaction product is difficultly soluble in the propylene carbonate and separates as a second phase above the propylene carbonate phase, or it can be extracted with pentane or another hydrocarbon.
• trans,trans,cis 13%
• trans,cis,cis 3%
• EXAMPLE 10 A solution of 7.9 g (30.8. mmoles)of nickel (ll) acetylacetonate, 32.9 g (185 mmoles) of diphenylacetylene and l.6 g of tetrabutylammonium bromide in 80 ml of THF are electrolyzedat 40C between two aluminum electrodes. Current: 45 volts, 0.4 A/dm During the electrolysis the initially green solution turns brown. After the passage of 1,950 mA.hours, 0.45 g of aluminum has dissolved from the anode, corresponding to 68% of theory. 50 ml of diethyl ether is added to the solution and the solution is filtered.
• iron ([11) acetylacetonate is used in 200 ml of pyridine in which 8.4 g of lithium chloride are dissolved as a conducting salt instead of the tetrabutyla mmoni urn bromide.
• the electrolysis is performed between two aluminum electrodes at C. Current: 30 mA 30 cm area of each electrode surface. After 61 hours of electrolysis 0.612 mg of aluminum has dissolved from the anode, corresponding to a current yield of 100%.
• a brown powder is obtained from the dark brown electrolyte solution after the pyridine has been removed by evaporation at 0C and 0.0001 mm Hg; it is bis-[cyclooctatetraenel-iron contaiminated bylithiurn chloride and aluminum tris-acetyl-acetonate.
• EXAMPLE 12 20C The rusty brown, powdery residue is extracted with warm benzene and thus free of conducting salt. Yield of tris-[cyclooctatetraene]-dimanganese: 1.6 g (3.8 mmoles), corresponding to 51% of theory.
• EXAMPLE 13 A solution of 6 g of vanadylacetylacetonate in 80 ml of tetrahydrofurane, to which 1.5 g of tetrabutylammonium bromide has been added as conducting salt, plus 4.1 g (40 mmoles) of cyclooctatetraene, is electrolyzed between aluminum electrodes, current 30 mA at 0.20 dm of surface per electrode, 40 volts, temperature 0 to C. The anodic current yield amounts to 65%. After evaporation of the solvent, bis- [cyclooctatetraene]-vanadium is obtained, contaminated by tetrabutylammon ium bromide.
• EXAMPLE 14 A solution of 2.0 g (7.8 mmoles) of cobalt (ll) acetylacetonate in ml of pyridine, in which 3.3 g of lithium chloride is dissolved as a conducting salt, along with 5 'g (46 mmoles) of cyclooctadiene-( 1,5) and 0.45 g (10 mmoles) of ethanol, is electrolyzed between two aluminum e lgc tro d es fo 20 hours at -5C and 30 mill ia'mperes 31"30 volts. 0.207 g of aluminum dissolve from the anode, corresponding to an anodic current yieldjof 100%.
• anodes of cobalt metal can be used instead of alu minium anodes.
• the anodic current yield then amounts to about 67 to 70 i
• the transition metal compounds may be present as salts of aliphatic acids such as acetic, atearic, benzoic, chloracetic, and the like; alkanolates such as those of methanol, butanol, ethyl hexanol, propanol, tert.
• butanol, and the like in addition to the illustrated ethylate; halides such as the bromide or iodide; and complexes with other Lewis bases such as triethyl phosphine, tricyclohexyl phosphine, or tri-ortho-phenyl-phenyl phosphite.
• Other complexing agents include isoprene.
• Other conducting salts include lithium bromide or iodide, tetrmethylammonium chloride, and tetrabutyl-tetraphenyl borate.
• the conducting salt is an ammonium salt, a tetraalkylammonium halide or a lithium halide.
• cathode of said cell comprises at least one of aluminum, mercury, lead, tin, graphite, iron, platinum, nickel or titanium.
• transition metal comprises at least one of titanium, chromium, iron, cobalt and nickel.
• the complexing agent is a cyclic polyolefin, a cyclic monoolefin with a strained double bond, a 1,3-diolefin or an alkyne.
• the complexing agent is a tertiary phosphine, phosphite, arsine or stibine.
• said solvent comprises an aromatic hydrocarbon, an aliphatic ether, propylene carbonate or pyridine.
• the cathode of said cell comprises at least one of aluminum, mercury, lead, tin, graphite, iron, platinum, nickel or titanium
• the anode and the transition metal whose organometallic complex is being produced comprises at least one of titanium, chromium, iron.
• the complexing agent is a cyclic polyolefin, a cyclic monoolefin with a strained double bond, a 1,3- diolefin, an alkyne, a tertiary phosphine, phosphite, arsine or stibine, said solvent comprising an aromatic hydrocarbon, an aliphatic ether, propylene carbonate or pyridine, said electrodes being spaced apart a distance of about 0.2 to 5 cm and the electrolysis being performed in the substantial absence of air and moisture at a temperature of about 20 to C.
• Process according to claim 13 including adding an olefin or alkyne to the electrolyte solution during electrolysis whereby a oligomer of said olefin or alkyne iss directly produced.

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• 1970
  • 1970-02-17 DE DE2007076A patent/DE2007076C3/de not_active Expired
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