WO2009036775A1

WO2009036775A1 - Process for preparing methyltrioxorhenium and organorhenium(vii) oxides

Info

Publication number: WO2009036775A1
Application number: PCT/EP2007/007990
Authority: WO
Inventors: Norman Szesni; Stefanie Sturm; Richard Fischer; Wolfgang Anton Herrmann
Original assignee: Süd-Chemie AG
Priority date: 2007-09-13
Filing date: 2007-09-13
Publication date: 2009-03-26
Also published as: EP2197891A1

Abstract

The invention relates to a process for preparing organorhenium(VII) oxides, especially methyltrioxorhenium, starting from perrhenates, by reacting them with an activating agent and with a functionalized organylating reagent.

Description

Process for the preparation of methyltrioxorhenium and organorhenium (VII) oxides

The present invention relates to a process for the preparation of organorhenium oxides, in particular methyltrioxorhenium, starting from perrhenates, by reacting them with an activating reagent and a functionalized organylating reagent.

Methyltrioxorhenium (VII) (MTO for short) is considered to be the parent compound of organorhenium (VII) oxides. IR Beattie and PJ Jones first reported on MTO in 1979 (Inorg Chem., 1979, 18, 2318). It is obtained in up to 50% yield from trimethyldioxorhenium (VI) (CH ₃ J ₃ ReO ₂ or tetramethyloxorhenium (VII) (CH ₃ J ₄ ReO), the starting materials having to be exposed to dry air for weeks in order to convert them to MTO to effect.

Due to the high time required, the very difficult to access precursors and the unsatisfactory product yields, this production process was of no importance. Instead, four alternative syntheses are common, which are the organylations of various rhenium (VII) precursors. These methods have been described by Herrmann et al. developed.

(1) By the process of direct alkylation of dirhenium heptoxide Re _Σ O _? (WA Herrmann et al., Angew Chem. 1988, 100, 420) is obtained with non-reducing transfer reagents such as tetraalkyltin R ₄ Sn in a smooth reaction, the corresponding organorhenium (VII) oxides. The main disadvantage of this process is that half of the rhenium used is obtained as a polymeric trialkylstannyl perrhenate. Thus, the maximum lies theoretically achievable yield at only 50% based on rhenium. The actual yield achieved is about 45%. If, instead of the toxic tin reagents R ₁ ) Sn, corresponding zinc reagents of the formula R ₂ Zn are used, they effect the alkylation but also the undesired reduction of the rhenium.

(2) In the so-called "anhydride route" (W.A. Herrmann et al., Inorg. Chem. 1992, 31, 4431), the alkylation is carried out with the mixed anhydrides of perrhenic acid and carboxylic acids. Here, dirhenium heptoxide is reacted successively with carboxylic anhydrides and tetraalkyltin compounds. When using halogenated carboxylic anhydrides (preferably trifluoroacetic anhydride), the yields are 80-90%, wherein the separation of the resulting (trialkylstannyl) carboxylic anhydrides from the MTO formed requires many steps and is therefore tedious. The described reaction remains limited to the few reactive tin compounds. This limits its synthetic bandwidth.

(3) According to a patented in 1998 process (Aventis US-A-6 180 807, DE-A-197 17 178) are inorganic or organometallic perrhenates with a silylating reagent (preferably trimethylsilyl chloride TMS-Cl) and an organylating reagent (usually tetraalkyltin R ₄ Sn or dialkylzinc R ₂ Zn) are converted to the corresponding organorhenium (VII) oxide. When using the difficult to access calcium perrhenate and tetramethyltin, the yield of MTO is 80%. In addition, silylation reagents are available at very high prices on the market. (4) In a further developed process, methylzinc acetate is used as a methylating reagent (Cata Tech

WO-A-2006/024493). This is a variant of the anhydride route. The Alkylierungsreagenz used has the advantage of lower toxicity and the lower price compared to the hitherto customary organotin, a better than those of the prior art

Handling and a smaller reduction effect of

Zinc organyls.

In all four processes MTO is only obtained in good

Yields, if as methylating reagent tin (IV) compounds

(Above all Sn (CH ₃ ) ₄ , CH ₃ Sn (n-CjHg) ₃ ) are used. This represents a significant disadvantage, since these very volatile compounds are acutely toxic and carcinogenic. Thus require

Synthesis and purification of organorhenium (VII) oxides a special work and equipment costs as well as a special

Laboratory or Technikumseinrichtung. They are intense

Occupational safety measures. Another disadvantage is the high price of tin organyls.

Although the dialkylzinc compounds which can be used in synthesis routes (1), (3) and (4) are less objectionable in terms of their toxicity, they have other disadvantages, so that production of organorhenium (VII) oxides in relatively large amounts is scarcely possible , Thus, the zinc alkyls are Zn ₂ R - especially _(CH3 J ₂ and Zn (CH ₃ CH ₂ J ₂ Zn -.. Spontaneously inflammable are achieved rarely good yields Further, the reaction must in each case (at very low temperatures -78 ⁰ C or lower), otherwise a reduction of the rhenium (VII) precursors to low-valent rhenium compounds occurs.The processing of such approaches is cumbersome and time-consuming, which leads to a significantly increased preparative effort and thus also to higher costs. The synthetic routes of the prior art also have the disadvantage that in the market little available and expensive

Rhenium compounds are used as starting materials in the process. Partially many rhenium compounds are known as

Starting materials are used, sensitive to moisture.

The object of the present invention was to provide a process for preparing organorhenium (VII) oxides, in particular methyltrioxorhenium, via readily available and moisture-insensitive rhenium-containing starting compounds, wherein the organorhenium (VII) oxides are to be obtained in high yields and with little work-up steps.

The object is achieved by a method for producing an organorhenium (VII) oxide by reacting a perrhenium oxide with an activating reagent and a functionalized Organylierungsreagenz, wherein the perrhenate consists of a compound of formula (I)

Z _n (ReO ₄ ) _m , (I) in which n and m assume values such that the compound is neutral to the outside, the organorhenium (VII) oxide of the formula (II) is formed R _a Re _b O _c L _d , (II) in the

R is an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic hydrocarbon radical having 6 to 20 atoms or arylalkyl radical having 7 to 20 atoms, where R may be identical or different or more than one radical R may be identical or different L can be a Lewis basic neutral ligand, and a is the number of R's and is 1 to 6, b is the number of rhenium atoms and is 1 to 4, c is the number of oxygen atoms and 1 to 13, d is the number of ligands and 0 to 6, wherein the sum of a, b and c is such the segregation of rhenium is satisfied provided that c is not greater than 4 times b, where Z is selected from a metal selected from the group consisting of an alkali metal, alkaline earth metal, rare earth metal and transition metal, or selected from a nitrogen or phosphorus containing cation consisting of ammonium, alkylammonium, phosphonium, alkylphosphonium and a cationic heterocyclic or heterobicyclic aromatic, or is selected from an organometallic III. or IV. Main Group of the Periodic Table of the Elements.

In the process according to the invention, the perrhenium oxide of the formula (I) initially reacts with the activating reagent to give a perrhenyl-containing compound of the formula (III)

O ₃ ReYLe, where e is an integer from 0 to 5,

L is a Lewis basic neutral ligand and

Y is a fragment of the activating reagent remaining after cleavage of its leaving group. The cation of the perrhenium oxide and the leaving group of the activating reagent usually form a salt which, if appropriate, precipitates and thereby promotes the formation of the compound of the formula III comprising perrhenyl function.

The person skilled in the art understands by a Lewis-basic neutral ligand a coordinated substituent which has no ionic charge to the outside and an electron pair has to coordinate with the rhenium-containing compound.

The perrhenyl-containing compound is then reacted with the functionalized organylating reagent to obtain the organorhenium (VII) oxide of formula II. In this case, the or the hydrocarbon radical (s) is transferred to the compound of the formula III.

It has surprisingly been found that the perrhenates of the formula I according to the invention are particularly suitable as starting materials. On the one hand, they are partly commercially easily accessible, on the other hand, they have been found to be particularly resistant to moisture Rheniumoxide. The perrhenium oxides used in the prior art sometimes have to be stored dry for weeks until they can be used for the production of organorhenium (VII) oxides. Therefore, perrhenates according to the invention have particular advantages over those of the prior art.

In a preferred method, the perrhenium oxide is selected from the group consisting of an alkali metal, alkaline earth metal, rare earth metal, transition metal, ammonium, alkylammonium, phosphonium, Alkylphosphoniumper- rheniumoxid Organometallperrheniumoxid III. or IV. Main group of the Periodic Table of the Elements and a perrhenium oxide wherein Z is a cationic heterocyclic or heterobicyclic aromatic, and the activating reagent is an aliphatic or aromatic carboxylic acid halide, carboxylic acid tosylate, carboxylic acid triflate, sulfonic acid halide, sulfonic acid tosylate or triflate or also anhydride of the acids used. This preferred embodiment of the process according to the invention, in which a combination of the perrhenium oxides used according to the invention and the selected activating reagents is used, offers several advantages. The combination of the perrhenium oxides and the activating reagents results in higher yields of the compound of formula III comprising perrhenyl function, since the cation of the perrhenium oxide and the leaving group of the activating reagent can be selected to precipitate a sparingly soluble by-product such that the equilibrium of the reaction the side of the perrhenyl functional compound is displaced. The precipitated by-product may be, for example, silver chloride when silver perrhenium oxide and a carboxylic acid chloride are used as the activating reagent.

In contrast to the anhydrides used in the prior art, the carboxylic acid or sulfonic acid halides as well as the corresponding tosylates and triflates are activating reagents which have per se excellent leaving groups.

A decisive advantage of all embodiments of the process according to the invention is that it is possible to dispense with expensive silylating agents as activating reagents. The erfindungsgmäßen process are therefore carried out without silylating.

In another preferred method, the organorhenium oxide is methyltrioxorhenium. This is prepared by the perrhenium oxide selected from an alkali metal, alkaline earth metal, rare earth metal, transition metal, ammonium, alkylammonium, phosphonium, alkyl phosphoniumperrheniumoxid, Organometallperrheniumoxid III. or IV. Main Group of the Periodic Table of the Elements and a perrhenium oxide wherein Z is a cationic heterocyclic or heterobicyclic aromatic is reacted with an aliphatic or aromatic carboxylic acid halide, carboxylic acid tosylate, carboxylic acid triflate or sulfonic acid halide and a functionalized organylating reagent.

The organorhenium (VII) oxide methyltrioxorhenium is the rhenium compound with the most desirable advantageous catalytic properties.

Particular preference is given to the process alkylammonium perrhenate having the formula [R ^ N] ReO _{3 used} as the activating reagent in which R 'is the same or different or bridged or unbridged and represents hydrogen or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms wherein the hydrocarbon radical contains 0 to 2 oxygen atoms. It is clear to the person skilled in the art that not all R 'can represent hydrogen, but always at least one R' represents a hydrocarbon radical. The hydrocarbon radical may be interrupted by one or two oxygen atoms, ie ether groups may be present. Very particular preference is given to using cetyltrimethylammonium perrhenate, lauryltrimethylammonium perrhenate, piperidinium perrhenate, pyrrolidinium perrhenate or morpholinium perrhenate as the activating reagent. It has surprisingly been found that these perrhenates are particularly insensitive to moisture.

Particularly preferred cationic heterocyclic or heterobicyclic aromatics as counterions of the perrhenates are selected from the group consisting of pyridinium, pyrrolium,

Imidazolium, pyrazolium, pyrimidinium, oxazolium, thiazolium,

Indolium, quinolinium, purinium. Surprisingly, it has been found that trimetyltin perrhenium oxide is particularly insensitive to moisture as an activating reagent from the field of organometallic perrhenium oxides.

Particularly suitable Metallperrheniumoxide silver, zinc, potassium, sodium, calcium and Magnesiumperrheniumoxid have been found. These perrhenium oxides are partly particularly cost-effective on the one hand. Furthermore, they offer the advantage, in part, that in the reaction of the perrhenium oxides with the activating reagent, an insoluble salt precipitates, so that this step of the process can be run at high conversions. In particular, the reaction of Silberperrheniumoxid with carboxylic acid or sulfonic acid chlorides is particularly preferred because of the formation of insoluble silver chloride.

In particularly preferred methods, the activating reagent is selected from acetic acid chloride, propionic acid chloride, isobutyric acid chloride, pivaloyl chloride, benzoic acid chloride, trichloroacetic chloride, trifluoroacetic acid chloride, acetic acid bromide, propionic acid bromide, isobutyric acid bromide, pivalic acid bromide, trichloroacetic acid bromide, trifluoroacetic acid bromide, acetic acid tosylate, propionic acid tosylate, isobutyric acid tosylate , Pivaloic tosylate, benzoic acid tosylate, trichloroacetic acid tosylate, trifluoroacetic acid tosylate, acetic acid triflate, propionic acid triflate, isobutyric acid triflate, pivalic triflate, benzoic acid triflate, trichloroacetic acid triflate, trifluoroacetic acid triflate, p-toluenesulfonyl chloride or trifluoromethylsulfonyl chloride. In contrast to the anhydrides used in the prior art, the carboxylic acid or sulfonic acid halides as well as the corresponding tosylates and triflates represent activating reagents which have excellent Leaving groups. These activating reagents are readily available commercially.

In a preferred embodiment of the process according to the invention Process according to one of the preceding claims, characterized in that the functionalized organylating reagent is a compound of the formula (III)

[R _f MX _g -L _n] ¹ (III) in which R represents an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, an aromatic hydrocarbon radical having 6 to 20 carbon atoms or arylalkyl having 7 to 20 atoms, wherein R when more than one R may be the same or different or may be the same or different, M is a metal selected from the group consisting of Zn, Al, Li, Mg, Ti, In, Ga, Cu, Sc, Y, La and Ce,

X is a halogen, cyclopentadienide, pseudohalogen, alkoxy, aryloxy, oxide, sulfide, acyloxy, alkanesulfanyloxy, arylsulfanyloxy, amino, alkylamino, arylamino substituent, wherein X is absent, the same or different, L is a Lewis basic neutral ligand, and f represents the number of R's and R is 1 to 6, g is the number of X's and Z is 0 or 1 to 6, h is the number of L's and is zero or 1 to 5, i is the charge and is zero or -1 to -4, with a negative charge balanced by any cation, and the sum of f, g and i being that of valence of the metal M.

The hydrocarbon radical R is ultimately formally based on the perrhenyl-containing compound of the formula (III) transferred to obtain the desired organorhenium (VII) oxide. In this case, the Y group of the perrhenyl-containing compound is separated. R is particularly preferably a methyl group, so that the particularly preferred methyltri oxorhenium is produced. It goes without saying that the hydrocarbon radical R in both formula I and in formula III can only be different or substituted differently if several radicals R are present. According to the invention, the substituents R are therefore either all the same or different R are contained in a compound.

Most preferably, the metal M is zinc, aluminum, lithium, magnesium or titanium. This is a non-toxic substitute for the toxic organotin reagents used in the art. The avoidance of toxic contaminations of the products is a further feature of the invention: The hitherto known preparation processes, in particular the parent substance MTO, were dependent on tin-containing alkylation or methylating agents

(For example, Sn (CH ₃ ) ₄ , CH ₃ Sn (n-CjHg) ₃ ), which appear as trace impurities in the products and therefore special

Precautions in the complicated product purification required. However, since the solubility in organic solvents and the volatility of product and toxic tin-containing contamination are comparable, previously a complete avoidance of impurities for methodological reasons were only possible under considerable time and effort. Thus, the method according to the invention in this respect also exceeds the state of the art in a fundamental way.

Zinc is particularly preferred as the metal, since zinc organyls have a particularly low toxic effect and the reactivity is matched to the compound containing the perrhenyl function.

Particularly preferably, the substituent X in formula IV is absent or an acyloxy, chlorine or bromine substituent. Also preferred are alkoxides and amides. Substituents on the group X are preferably selected from C 1 -C 6 alkyl radicals, e.g. Methyl or ethyl, and C6-C10-aryl radicals selected, wherein the alkyl radicals may optionally be mono- or polysubstituted by halogen, hydroxyl, Cl-C4-alkoxy and / or Cβ-ClOAryl and the aryl radicals optionally in turn with halogen, hydroxyl and / or C 1 -C 4 -alkyl may be substituted. Acyloxy radicals are preferably the radicals of C 1 -C 6 -alkyl or C 6 -C 10 -arylcarboxylic acids, where alkyl and aryl may be substituted as indicated above.

The radicals R preferably have the meanings as for

Compounds (II) indicated. R is more preferably selected from methyl, ethyl, propyl, cyclopropyl, phenyl, mesityl, cyclopentadienyl and chloromethyl.

Due to the variable design of the substituent X, the reactivity and solubility of the alkylating reagent can be adapted very precisely to the reaction conditions and the respective rhenium precursor. How crucial the exact choice of the alkylating reagent is for the synthesis success is shown by e.g. The reaction of Re2O7 with Zn (CH3) 2 is known to produce reduced products such as (CH3) 4Re2O4, while CH3Zn (OAc) or CH3ZnCl gives only the most preferred CH3ReO3 (MTO).

Very particular preference is given to the functionalized organylating reagents selected from methylzinc chloride, dimethylzinc, methylzinc acetate, methyllithium, methylmagnesium, nesium chloride, methylmagnesium bromide, trimethylaluminum, methyltitanium tris (isopropylate), methylcuprate, methylcerchloride, methylzinc isopropylate or methylzinc-tert. butylate. The reagents mentioned are readily available and low in toxicity.

The conversion to organorhenium (VII) oxides is carried out in a one-pot reaction in organic solvents, in coordinating organic solvents. The ligand L thus acts as a coordinated ligand as well as a solvent. It has surprisingly been found that acetonitrile, tetrahydrofuran, diethyl ether, tert-butyl ether, dioxane and toluene, in particular acetonitrile or mixtures of said ligands are particularly suitable for the process according to the invention. Particularly preferably, the reaction takes place in the donor solvents acetonitrile or tetrahydrofuran. The choice of solvent also indirectly determines the duration of the process. If resulting by-products (such as zinc diacetate or silver chloride) precipitate in the selected solvents, costly separation steps are saved.

The reaction temperature varies depending on the starting materials used between -115 and +110 ⁰ C, preferably room temperature (25 ⁰ C). The reaction is preferably carried out in the absence of water.

The organorhenium (VII) oxide is preferably used as a catalyst. Preferred areas for industrial use of organorhenium (VII) oxides include MTO-catalyzed olefin epoxidation and MTO-catalyzed aromatic oxidation (Arco Chemicals US-A-5 166 372; Hoechst AG DE-A-3 902 357, EP-A-90 101 439.9). MTO is converted by hydrogen peroxide H ₂ O ₂ gradually via a mono (peroxo) - into a bis (peroxo) rhenium complex. The latter is the most efficient catalyst for the epoxidation of olefins.

Further preferred fields of use are the catalysis of aromatic oxidation (Hoechst AG DE-A-44 19 799.3), olefin

Isomerization and olefin metathesis (BASF AG DE-A-42 28 887;

Hoechst AG DE-A-39 40 196, EP-A-891 224 370), carbonyl

Olefination (Hoechst AG DE-A-4 101 737), Bayer-Villiger

Oxidation, Diels-Alder reaction and the oxidation of metal carbonyls, sulfides and many other organic and inorganic substrates. An overview: C. C. Romão,

E.K. Kühn, W.A. Herrmann, Chem. Rev. 1997, 97, 3197-3246.

In addition, the organorhenium (VII) oxide may also be used to produce high purity rhenium oxides, e.g. be used according to a CVD (Chemical Vapor Deposition) method.

Furthermore, the invention will be explained in more detail with reference to the following example.

Example: Method for the preparation of methyltrioxorhenium

To a solution of 2.0 g (5.59 mmol) of silver perrhenate in 40 ml of acetonitrile, 0.44 g (5.59 mmol) of acetyl chloride are added dropwise at 0 ° C. with stirring. Almost immediately, silver chloride precipitates as a fuzzy colorless precipitate. The suspension is stirred for a further 10 min at this temperature. The precipitated silver chloride is filtered off and the resulting clear, slightly yellowish solution is admixed at room temperature with a slight excess (about 1.1 equivalents) of methyl zinc acetate. The initially clear solution separates a white precipitate of zinc acetate. After about 5 hours at this temperature, the precipitated solid is filtered off and the solvent of the Filtrate removed. The residue is taken up in 100 ml of n-hexane, the insoluble residue is separated off, the solvent is removed and the residue is sublimed in vacuo. There are obtained 1.32 g (5.31 mmol, 95%) of methyltrioxorhenium as a pure white, analytically pure solid.

Claims

claims

A process for preparing an organorhenium (VII) oxide by reacting a perrhenium oxide with an activating reagent and a functionalized organylating reagent, said perrhenium oxide being selected from a compound of the

Formula (I) exists

Z _n (ReO ₄ ) _m , (I) in the n and m values assume, so that the compound is neutral to the outside, wherein the organorhenium (VII) oxide of the formula (II) is formed

R _a Re _b O _c L _d , (II) in the

R is an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic hydrocarbon radical having 6 to 20 atoms or arylalkyl radical having 7 to 20 atoms, where R can be identical or different or can be substituted identically or differently with more than one radical R, L is a Lewis basic neutral ligand, and in which a represents the number of R's and is 1 to 6, b represents the number of rhenium atoms and 1 to 4, c represents the number of oxygen atoms and 1 to 13, d represents the number of ligands and is 1 to 6, the sum of a, b and c being such that it satisfies the segregation of rhenium with the proviso that c is not greater than 4 times b, characterized in that Z is selected from a metal selected from the group consisting of an alkali metal, alkaline earth metal, rare earth metal and transition metal, or is selected from a nitrogen or phosphorus containing Cation consisting of ammonium, alkylammonium, phosphonium, alkylphosphonium and a cationic heterocyclic or heterobicyclic Aromatic, or is selected from an organometallic III. or IV. Main Group of the Periodic Table of the Elements.

2. The method according to claim 1, characterized in that Z is selected from a metal selected from the group consisting of an alkali metal, alkaline earth metal, rare earth metal and transition metal, or is selected from a nitrogen or phosphorus-containing cation consisting of ammonium, alkylammonium, phosphonium, alkylphosphonium and a cationic heterocyclic or heterobicyclic aromatic, or is selected from an organometallic of III. or IV. Main Group of the Periodic Table of the Elements, and the activating reagent is an aliphatic or aromatic carboxylic acid halide, carboxylic acid tosylate, carboxylic acid triflate or sulfonic acid halide.

3. Process according to claim 1 or claim 2, characterized in that the organorhenium (VII) oxide is methyltrioxorhenium which is prepared by reacting the perrhenium oxide selected from an alkali metal, alkaline earth metal, rare earth metal, transition metal, Ammonium, alkylammonium, phosphonium, Alkylphosphoniumperrhenium- oxide, Organometallperrheniumoxid III. or IV. Main group of the Periodic Table of the Elements and a perrhenium oxide in which Z is a cationic heterocyclic or heterobicyclic aromatic is reacted with an aliphatic or aromatic carboxylic acid, Carbonsäuretosylat, Carbonsäuretriflat or sulfonic acid halide and a functionalized Organylierungsreagenz.

4. The method according to any one of claims 1 to 3, characterized in that the Z has the formula [R ₄ N] ⁺ , in which R 'is the same or different or bridged or unbridged is and is hydrogen or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, wherein the hydrocarbon radical contains 0 to 2 oxygen atoms.

5. The method according to claim 4, characterized in that Z is selected with the formula [R ' ₄ N] ⁺ from the group cetyltrimethylammonium, lauryltrimethylammonium, piperidinium, pyrrolidinium and morpholinium.

6. The method according to any one of claims 1 to 3, characterized in that the cationic heterocyclic or heterobicyclic aromatic is selected from the group consisting of pyridinium, pyrrolium, imidazolium, pyrazolium, pyrimidinium, oxazolium, thiazolium, indolium, quinolinium, purinium.

7. The method according to any one of claims 1 to 3, characterized in that the organometallic is trimethyltin.

8. The method according to any one of claims 1 to 3, characterized in that the alkali metal, the alkaline earth metal or the transition metal is selected from the group consisting of silver, zinc, potassium, sodium, calcium and magnesium.

9. The method according to any one of the preceding claims, characterized in that the activating reagent is selected from the group consisting of acetic acid chloride, propionic acid chloride, isobutyric acid chloride, pivaloyl chloride, benzoic acid chloride, trichloroacetic acid chloride, trifluoroacetic acid chloride, acetic acid bromide, propionic acid bromide, isobutyric acid bromide, pivalic acid bromide, benzoic acid bromide, trichloroacetic acid bromide, trifluoroacetic acid bromide, acetic acid tosylate, propionic acid tosylate, isobutyric acid tosylate, pivalic acid tosylate, benzoic acid tosylate, trichloro acetic acid tosylate, trifluoroacetic acid tosylate, acetic acid triflate, propionic triflate, isobutyric triflate, pivalic triflate, benzoic triflate, trichloroacetic acid triflate, trifluoroacetic acid triflate, p-toluenesulfonic acid chloride and trifluoromethylsulfonic acid chloride.

10. The method according to any one of the preceding claims, characterized in that the functionalized organylating reagent is a compound of formula (III) [R _f MX _g -L _h ] ¹ (III), in which

R is an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic hydrocarbon radical having 6 to 20 atoms or arylalkyl radical having 7 to 20 atoms, where R can be identical or different or can be substituted identically or differently with more than one radical R,

M is a metal selected from the group consisting of Zn, Al, Li, Mg, Ti, In, Ga, Cu, Sc, Y, La and Ce, X is a halogen, cyclopentadienide, pseudohalogen, alkoxy, aryloxy , Oxide, sulfide, acyloxy, alkanesulfanyloxy, arylsulfanyloxy, amino, alkylamino, arylamino substituent, wherein X is absent, the same or different, L is a Lewis basic neutral ligand, and in the f is the number of R's and is 1 to 6, g is the number of X groups and is zero or 1 to 6, h is the number of L's and is zero or 1 to 5, i is the charge and zero or Is -1 to -4, with a negative charge balanced by any cation, and the sum of f, g and i is such as to satisfy the valency of the metal M.

11. The method according to claim 10, characterized in that M is Zn, Al, Li, Mg, Ti, Cu or Ce and R is methyl and X is absent or an acyloxy, chlorine or bromine substituent.

12. The method according to claim 10, characterized in that the functionalized organylating reagent is selected from methylzinc chloride, dimethylzinc, methylzinc acetate, methyl lithium, methylmagnesium chloride, methylmagnesium bromide, trimethylaluminum, methyltitanium tris (isopropylate), methylcuprate and methylcerchloride.

13. The method according to any one of the preceding claims, characterized in that the Lewis basic neutral ligand is selected from the group consisting of acetonitrile, tetrahydrofuran, diethyl ether, tert-butyl ether, dioxane and toluene, in particular acetonitrile.

14. The method according to any one of the preceding claims, characterized in that the activating reagent is not a silylating agent.

15. Use of organorhenium (VII) oxide prepared as claimed in any one of claims 1 to 14 as a catalyst.

16. Use according to Claim 15, characterized in that the organorhenium (VII) oxides are an aromatic oxidation, an olefin isomerization, an olefin metathesis, a carbonyl olefination, a Bayer-Villiger oxidation, a Diels-Alder reaction or catalyzes oxidation of metal carbonyls or sulfides.

17. Use of the organorhenium (VII) oxide prepared according to any one of claims 1 to 14 for the production of rhenium oxides by the CVD method.