METAL ORGANIC COMPOUNDS

Abstract

The invention concerns a process for preparing an essentially silicon (Si) free compounds of the general formula [M(O)(OR).sub.y], wherein M = Mo, y = 3 or M = W, y = 3 or 4. Furthermore, it is directed towards compounds obtained by the aforementioned process and towards the use of such an obtained compound. Another objective of the herein described invention are essentially silicon free compounds of the general formula MOX.sub.y or [MOX.sub.y(solv).sub.p], prepared using the aforementioned process, wherein M = Mo, y = 3 or M = W, y = 3 or 4, X = Cl or Br, solv = an oxidizing agent Z binding or coordinating to M via at least one donor atom, p = 1 or 2. The invention is also directed towards the use of essentially silicon free compounds prepared using the aforementioned process of the general formula MOX.sub.y or [MOX.sub.y(solv).sub.p],

Claims

1. A process for preparing an essentially silicon (Si) free compound of the general formula ##STR00006## wherein M = Mo and y = 3 or M = W and y = 3 or 4 and R is selected from the group consisting of a linear, branched or cyclic alkyl group (C1 -C10), a linear, branched or cyclic partially or fully halogenated alkyl group (C1 - C10), an alkylene alkyl ether group (R.sup.E-O).sub.n-R.sub.F, a benzyl group, a partially or fully substituted benzyl group, a monocyclic or polycyclic aryl group, a partially or -fully substituted monocyclic or polycyclic aryl group, a monocyclic or polycyclic heteroaryl group and a partially or fully substituted monocyclic or polycyclic heteroaryl group, wherein R.sup.E are independently from each other selected from the group consisting of a linear, a branched or a cyclic alkylene group (C1 - C6) and a linear, a branched or a cyclic partially or fully halogenated alkylene group (C1 - C6), R.sup.F are independently from each other selected from the group consisting of a linear, a branched or a cyclic alkyl group (C1 - C10) and a linear, a branched or a cyclic partially or fully halogenated alkyl group (C1 - C10), a substituted or unsubstituted aryl group (C6 - C11), and n = 1 to 5 or 1, 2 or 3, comprising the steps of a) reacting a compound of the general formula MX.sub.y+2 wherein M and y are defined as above and X = Cl or Br, with an essentially silicon (Si) free oxidizing agent Z comprising 1 to 10 carbon atoms at a molar ratio of MX.sub.y+2 to the oxidizing agent Z of at least 1 : 0.75 in at least one aprotic solvent A, b) addition of an alcohol ROH, wherein R is defined as above, a molar ratio of MX.sub.y+2 to the alcohol ROH is at least 1 : 4, and ROH is different from the oxidizing agent Z of step a), c) supply of at least one essentially silicon (Si) free base.

2. The process according to claim 1, wherein the essentially silicon-free oxidizing agent Z is selected from the group consisting of alcohols, ketones, ethers, and mixtures thereof.

3. The process according to claim 1, wherein the essentially silicon-free oxidizing agent Z comprises 1 to 8 carbon atoms or 1 to 6 carbon atoms or 1 to 4 carbon atoms.

4. The process according to claim 1, wherein the molar ratio of MX.sub.y+2 to the essentially silicon-free oxidizing agent Z is in the range of 1 : 0.75 to 1 : 2.50 or in the range of 1 : 0.80 to 1 : 1.50 or in the range of 1 : 0.85 to 1 : 1.30.

5. The process according to claim 1, wherein MX.sub.y+2 is applied as a solid, a saturated solution in the aprotic solvent A, a suspension in the aprotic solvent A or as a solution in the aprotic solvent A or in a solvent miscible with the solvent A.

6. The process according to claim 1, wherein the neat essentially silicon-free oxidizing agent Z or a solution of the essentially silicon-free oxidizing agent Z in the aprotic solvent A or in a solvent miscible with the aprotic solvent A is applied.

7. The process according to claim 1, wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, sec-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2-methylbut-2-yl, 3-methylbut-2-yl, neopentyl, hexyl, 1-hexyl, 2-hexyl,3-hexyl,2-methylpent-1-yl, 3-methylpent-1-yl, 4-methylpent-1-yl, 2-methylpent-2-yl, 3-methylpent-2-yl, 4-methylpent-2-yl, 2-methylpent-3-yl, 3-methylpent-3-yl, 2,2-dimethylbut-1-yl, 2,3-dimethylbut-1-yl, 3,3-dimethylbut-1-yl, 2,3-dimethylbut-2-yl, 3,3-dimethylbut-2-yl, 2-ethylbut-1-yl, phenyl, benzyl, toluyl, mesityl, naphthyl and mixtures thereof.

8. Process according to claim 1, wherein the alcohol is selected from the group consisting of a monoethylene glycol monoalkyl ether, a diethylene glycol monoalkyl ether, a triethylene glycol monoalkyl ether, a monopropylene glycol monoalkyl ether, a dipropylene glycol monoalkyl ether, a tripropylene glycol monoalkyl ether, a monooxomethylene monoalkyl ether, a dioxomethylene monoalkyl ether and a trioxomethylene monoalkyl ether, a mixture of isomers thereof, and mixtures thereof, or when R corresponds to the formula (R.sup.E-O).sub.n-R.sub.F, then R.sup.E is selected from the group consisting of methenyl (—CH.sub.2—), ethenyl (—CH.sub.2CH.sub.2—), propenyl (—CH.sub.2CH.sub.2CH.sub.2—), isopropenyl (—CH(CH.sub.3)CH.sub.2—), n-butenyl (—CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), pentenyl (—CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—), hexenyl (—CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—) and mixtures thereof and R.sup.F is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, sec-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2-methylbut-2-yl, 3-methylbut-2-yl, neopentyl, hexyl, 1-hexyl, 2-hexyl,3-hexyl, 2-methylpent-1-yl, 3-methylpent-1-yl, 4-methylpent-1-yl, 2-methylpent-2-yl, 3-methylpent-2-yl, 4-methylpent-2-yl, 2-methylpent-3-yl, 3-methylpent-3-yl, 2,2-dimethylbut-1-yl, 2,3-dimethylbut-1-yl, 3,3-dimethylbut-1-yl, 2,3-dimethylbut-2-yl, 3,3-dimethylbut-2-yl, 2-ethylbut-1-yl, phenyl, benzyl, toluyl, mesityl, naphthyl and mixtures thereof.

9. Process according to claim 1, wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-ethyl-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-propyl-1-heptanol, 2-butyl-1-octanol, sBuCH.sub.2—OH, iBuCH.sub.2—OH, (iPr)(Me)CH—OH, (nPr)(Me)CH—OH, (Et).sub.2CH—OH, (Et)(Me).sub.2C—OH, C.sub.6H.sub.11—OH, benzyl alcohol C.sub.6H.sub.5CH.sub.2—OH, phenol C.sub.6H.sub.5OH, ethylene glycol monomethyl ether CH.sub.3—O—CH.sub.2CH.sub.2—OH, ethoxy ethanol CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2CH.sub.2—OH, ethylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2—OH, ethylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monomethyl ether CH.sub.3—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, propylene glycol monomethyl ether CH.sub.3—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2—C(CH.sub.3)—OH, propylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, iso-propylene glycol monomethyl ether CH.sub.3—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2—C(CH.sub.3)—OH, dipropylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH(CH.sub.3)OCH.sub.2CH(CH.sub.3)OH, iso-propylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, dipropylene glycol monomethyl ether CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH (mixture of isomers where appropriate), 1-methoxy-2-propanol CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OH, tripropylene glycol monomethyl ether CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH, dipropylene glycol monobutyl ether C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH, 1-butoxy-2-propanol C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OH, tripropylene glycol monobutyl ether C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH, 1-propoxy-2-propanol C.sub.3H.sub.7OCH.sub.2CH.sub.2CH.sub.2OH, a mixture of isomers thereof, and mixtures thereof.

10. The process according to claim 1, wherein the at least one essentially silicon-free base is selected from the group consisting of organic, organometallic and inorganic bases, and mixtures thereof.

11. The process according to claim 10, wherein the at least one essentially silicon-free base is selected from the group consisting of amines, ammonia, heterocyclic nitrogenous bases, alkali metal oxides and alkali metal amides, and mixtures thereof.

12. The process according to claim 1, wherein the supply of at least one essentially silicon (Si) free base according to step c) includes the options of adding the essentially silicon-free base by introducing a gas or a liquid or a solid, each being or comprising the at least one essentially silicon-free base, by introducing a solution comprising the at least one essentially silicon-free base or by pressurisation of the respective essentially silicon-free base in a pressure vessel.

13. The process according to claim 1, wherein a pressure pR is in the range of 1013.25 hectopascal (hPa) to 6000 hectopascal (hPa) or in the range of 1500 hectopascal (hPa) to 3000 hectopascal (hPa).

14. The process according to claim 1, wherein the aprotic solvent A is selected from the group consisting of linear or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbons, partly or fully halogenated linear or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbons, ether, benzene and benzene derivatives, and mixtures thereof.

15. The process according to claim 1, wherein step a), step b) or both comprise a distillation.

16. The process according to claim 1, wherein the reaction according to step a) comprises the steps of i. providing a solution or suspension of MX.sub.y+2 in the aprotic solvent A, ii. addition of the essentially silicon-free oxidizing agent Z, wherein during the addition and/or after the addition of the essentially silicon-free oxidizing agent Z a reaction between MX.sub.y+2 and the essentially silicon-free oxidizing agent Z occurs.

17. The process according to claim 1, wherein a temperature T.sub.R is in the range of -100° C. to 200° C. or in the range of -90° C. to 170° C. or in the range of -20° C. to 140° C.

18. The process according to claim 1, wherein the molar ratio of MX.sub.y+2 to the alcohol ROH ranges from 1 : 3 for y = 3, or from 1 : 4 for y = 4 to 1 : 40 for y = 3 or 4.

19. The process according to claim 1, wherein a temperature Tc ranges from -30° C. to 50° C. during and/or after the addition of the alcohol ROH.

20. The process according to claim 1, wherein a temperature T.sub.N ranges from -30° C. to 100° C. during and/or after the supply of at least one silicon (Si) free base.

21. The process according to claim 20, wherein a temperature T.sub.N1 ranges from -30° C. to 20° C. during a first phase of the supply of the at least one silicon (Si) free base and a temperature T.sub.N2 ranges from 21° C. to 100° C. during and/or after a second phase of the supply of the at least one silicon (Si) free base.

22. The process according to claim 1, wherein after step a) a reaction step is conducted comprising a removal of volatile by-products and/or solvent.

23. The process according to claim 1, wherein after step c) a reaction step d) is conducted comprising an isolation of the compound of the general formula [M(O)(OR).sub.y] (I).

24. Compounds of the general formula [M(O)(OR).sub.y] (I) having a silicon content of 1000 ppm or less, obtained by the process according to claim 1.

25. A process for preparing an essentially silicon (Si) free compound of the general formula ##STR00007## or ##STR00008## wherein M = Mo and y = 3 or M = W and y = 3 or 4, X=Cl or Br, solv = an oxidizing agent Z binding or coordinating to M via at least one donor atom and p = 1 and y = 4 or p = 2 and y = 3, the process comprising the steps of a) providing a compound of the general formula MX.sub.y+2 and b) reacting MX.sub.y+2 with at least one essentially silicon (Si) free oxidizing agent Z comprising 1 to 10 carbon atoms at a molar ratio of MX.sub.y+2 to the oxidizing agent Z of at least 1 : 0.75 in at least one aprotic solvent A.

26. The process according to claim 25, wherein the essentially silicon-free oxidizing agent Z is selected from the group consisting of alcohols, ketones, ethers, and mixtures thereof.

27. The process according to claim 25, wherein the molar ratio of MX.sub.y+2 to the essentially silicon-free oxidizing agent Z is preferably in the range of 1 : 0.75 to 1 : 2.50, more preferably in the range of 1 : 0.80 to 1 : 1.50 and most preferably in the range of 1 : 0.85 to 1 : 1.30.

28. The process according to claim 25, wherein MX.sub.y+2 is applied as a solid, a saturated solution in the aprotic solvent A a suspension in the aprotic solvent A or as a solution in the aprotic solvent A or in a solvent miscible with the solvent A.

29. The process according to claim 25, wherein the neat essentially silicon-free oxidizing agent Z or a solution of the essentially silicon-free oxidizing agent Z in the solvent A or in a solvent miscible with the solvent A is applied.

30. The process according to claim 25, wherein a temperature T.sub.R is in the range of -100° C. to 200° C., preferably in the range of -90° C. to 170° C., more preferably in the range of -20° C. to 140° C.

31. The process according to claim 25, wherein after step b) a reaction step c) is conducted, the step c) comprising i. a separation of by-products and/or ii. an isolation of the compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III).

32. The process according to claim 25, wherein the reaction mixture from step a) and the isolated compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III) contain 1000 ppm (thousand) or less or 50 ppm or less or 10 ppm (ten) or less or 1.500 ppb (fifteen hundred) or less, silicon each, wherein the silicon content is determined by inductively coupled plasma optical emission spectrometry.

33. Essentially silicon (Si) free compounds of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III), obtained by the process according to claim 25.

34. A solution or suspension comprising a compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III), obtained by the process according to claim 25.

35. Use of an essentially silicon (Si) free compound of the general formula ##STR00009## or ##STR00010## or of an essentially silicon (Si) free solution or suspension comprising the essentially silicon (Si) free compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III), obtained by the process according to claim 25 for preparing an essentially silicon (Si) free compound of the general formula [M(O)(OR).sub.y] (I).

36. A process for preparing an essentially silicon (Si) free compound of the general formula ##STR00011## using an essentially silicon (Si) free compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III) or an essentially silicon (Si) free solution or suspension comprising the essentially silicon (Si) free compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III), wherein M = Mo and y = 3 or M = W and y = 3 or 4, X=Cl or Br, solv = an oxidizing agent Z binding or coordinating to M via at least one donor atom p = 1 and y = 4 or p = 2 and y = 3 and R is selected from the group consisting of a linear, branched or cyclic alkyl group (C5 -C10), a linear, branched or cyclic partially or fully halogenated alkyl group (C5 - C10), an alkylene alkyl ether group (R.sup.E-O).sub.n-R.sup.F, a benzyl group, a partially or fully substituted benzyl group, a monocyclic or polycyclic arene, a partially or fully substituted monocyclic or polycyclic arene, a monocyclic or polycyclic heteroarene and a partially or fully substituted monocyclic or polycyclic heteroarene, wherein R.sup.E are independently from each other selected from the group consisting of a linear, a branched or a cyclic alkylene group (C1 - C6) and a linear, a branched or a cyclic partially or fully halogenated alkylene group (C1 - C6), R.sup.F are independently from each other selected from the group consisting of a linear, a branched or a cyclic alkyl group (C1- C10) and a linear, a branched or a cyclic partially or fully halogenated alkyl group (C1 - C10), and n = 1 to 5 or 1, 2 or 3, obtained by the process according to claim 24 comprising the steps of a) providing the essentially silicon (Si) free compound of the general formula MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III) prepared by the aforementioned process b) addition of an alcohol ROH, wherein R is defined as above and a molar ratio of MOX.sub.y (II) or [MOX.sub.y(solv).sub.p] (III) to the alcohol ROH is at least 1 : 3, c) supply of at least one essentially silicon (Si) free base, wherein step a) or b) may optionally comprise a distillation.

37. Essentially silicon (Si) free compounds of the general formula [M(O)(OR)y] (I) obtained by the process according to claim 36.

Description

EXAMPLES

General Experimental Remarks

Materials and Methods

[0301] Reactions were performed in a three-neck round-bottom flask or a stirred reactor, under an inert gas atmosphere and under continuous stirring at an internal temperature of the reactor given in the synthesis procedures below. A cryostat was used to control and/or regulate the internal temperature of the reactor.

[0302] The applied solvents were dried according to standard procedures.

Product Characterization

[0303] Identity of the isolated products WOCl.sub.4 and [WOCl.sub.4(solv)], respectively, was determined by X-ray diffraction (XRD) combined with W content determination. Purity of the isolated products - with respect to trace metals, in particular silicon (Si), - was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The determined silicon (Si) values are equal to or even lower than the limit of determination being 1.500 ppb.

[0304] Identity of the isolated products according to the general formula [W(O)(OR).sub.y] (l) was determined by nuclear magnetic resonance (NMR) spectroscopy. Purity of these products was determined by elemental analysis, NMR, W content and Cl content determination, trace metals analysis with an ICP-OES.

Synthesis of WOCl.SUB.4 and [WOCl_4.(L)]

Example 1: Preparation of WOCl.SUB.4 From WCl.SUB.6 and Acetone; Solvent: Dichloromethane

[0305] 10 g tungsten(VI) chloride (25.21 mmol, 1.00 eq.) are suspended and partly dissolved, respectively, in 50 mL dichloromethane. Subsequently, 1.464 g acetone (25.21 mmol, 1.00 eq.) dissolved in 20 mL dichloromethane are added within about 10 min by using a dropping funnel. During the addition of the acetone/dichloromethane mixture the internal temperature is held in the range 20° C. ± 5° C. After completion of the addition the dropping funnel is rinsed with 2 mL dichloromethane. Afterwards the reaction mixture is stirred for 2 h. The precipitate is separated by filtration and washed twice with 25 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) 7.82 g (90.78 %) of the desired essentially silicon-free product WOCl.sub.4 are isolated.

Example 2: Preparation of WOCl.SUB.4 From WCl.SUB.6 and Acetone; Solvent: Heptane

[0306] 100 g tungsten(VI) chloride (252.15 mmol, 1.00 eq.) are dosed into a 1 L stirred reactor by a solid substances metering funnel. Afterwards the metering funnel is rinsed with 300 mL heptane, whereby the tungsten(VI) chloride is suspended and partly dissolved, respectively. A mixture of 14,644 g acetone (252.15 mmol, 1.00 eq.) and 200 mL heptane was added by a dropping funnel over a period of about 1 h. During this time the internal temperature was held in the range of 19° C. to 26° C. After completion of the addition the reaction mixture was heated to 30° C. for 2.5 h. After cooling to ambient temperature the precipitate is filtered off over a glass frit (D4) and washed twice with 100 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) for 4 h the desired essentially silicon-free product WOCl.sub.4 is isolated as an orange solid in a yield of 83.12 g (96.49%).

Example 3: Preparation of WOCl.SUB.4 From WCl.SUB.6 and Tert-Butanol; Solvent: Heptane

[0307] 10 g tungsten(VI) chloride (25.21 mmol, 1.00 eq.) are suspended and partly dissolved, respectively, in 50 mL heptane. 1.888 g tert-butanol (25.21 mmol, 1.00 eq.) mixed with 20 mL heptane are dosed into the reaction vessel by a dropping funnel over a period of about 10 min. Thereby the internal temperature increases slightly. After completion of the addition the reaction mixture is stirred for another 4 h at ambient temperature. Subsequently, the precipitate is separated over a glass frit (D4) and washed twice with 10 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) the desired essentially silicon-free product WOCl.sub.4 is isolated as an orange solid in a yield of 8.12 g (94.26%).

Example 4: Preparation of WOCl.SUB.4 From WCl.SUB.6 and Methyl Tert-Butyl Ether; Solvent: Heptane

[0308] 10 g tungsten(VI) chloride (25.21 mmol, 1.00 eq.) are suspended and partly dissolved, respectively, in 50 mL heptane. 2,245 g methyl tert-butyl ether (MTBE) (25.21 mmol, 1.00 eq.) mixed with 20 mL heptane are dosed into the reaction vessel by a dropping funnel over a period of about 5 min. After completion of the addition the reaction mixture is stirred for another 16 h at ambient temperature. The precipitate is filtered off over a glass frit (D4) and washed twice with 25 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) the desired essentially silicon-free product WOCl.sub.4 is isolated as an orange solid in a yield of 8.11 g (94.14%).

Example 5: Preparation of WOCl.SUB.4 From WCl.SUB.6 and Methanol; Solvent: Dichloromethane

[0309] 10 g tungsten(VI) chloride (25.21 mmol, 1.00 eq.) are suspended and partly dissolved, respectively, in 50 mL dichloromethane. 0.808 g MeOH (25.21 mmol, 1.00 eq.) mixed with 20 mL dichloromethane are dosed into the reaction vessel by a dropping funnel over a period of about 15 min. Subsequently, the reaction mixture is stirred for 4 h at ambient temperature and then heated under reflux for about 80 min. After cooling to ambient temperature the precipitate is separated over a glass frit (D4) and washed twice with 25 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) the desired essentially silicon-free product WOCl.sub.4 is isolated as an orange solid in a yield of 6.35 g (73.71%).

Example 6: Preparation of [WOCl.SUB.4.(Acetone)] From WCl.SUB.6 and Acetone; Solvent: Heptane

[0310] 10 g tungsten(VI) chloride (25.21 mmol, 1.00 eq.) are suspended and partly dissolved, respectively, in 50 mL heptane. Subsequently, 2.93 g acetone (50.43 mmol, 2.00 eq.) dissolved in 20 mL dichloromethane are added within about 10 min by using a dropping funnel. During the addition of the acetone/dichloromethane mixture the internal temperature is held in the range 20° C. ± 5° C. After completion of the addition the dropping funnel is rinsed with 2 mL heptane. Afterwards the reaction mixture is stirred for 16 h. The precipitate is separated by filtration and washed twice with 25 mL heptane each. After vacuum drying (900 mbar to 10-.sup.3 mbar) 8.63 g (86.04%) of the desired essentially silicon-free product [WOCl.sub.4(acetone)] are isolated as yellow crystalline solid.

Synthesis of [W(O)(OR).SUB.4.] With NH.SUB.3 Starting From WCl.SUB.6

Examples 7 to 10: Preparation of [W(O)(OR).SUB.4]

[0311] The reactor was dried under vacuum at 60° C. for 1 hour. Heptane and the corresponding alcohols, glycol ether and polyglycol ether were dried over molecular sieve for several days according to standard methods.

[0312] Under inert gas atmosphere 100 g tungsten(VI) chloride (252.15 mmol; 1.0 eq.) are dosed into a 1 L stirred reactor by a solid substances metering funnel. Subsequently, tungsten(VI) chloride is suspended and partly dissolved, respectively, in 500 mL heptane (anhydrous) and the reaction mixture is stirred at ambient temperature. 14.66 g acetone (252.15 mmol, 1.0 eq.) in 200 mL heptane are added over a period of about 1 h. The reaction mixture is stirred for 16 h at ambient temperature, whereby a bright orange reaction mixture is obtained. To the WOCl.sub.4 slurry stirred at about 20° C. the corresponding alcohol or glycol ether or polyglycol ether is added slowly over a period of about 1 h. During the addition of the corresponding alcohol or glycol ether or polyglycol ether the precipitate is slowly dissolved and the colour of the reaction mixture changes to yellow (sBuOH or glycol ether or polyglycol ether) or decolorates

[00001]$\left(i\text{PrOH}\right).$

Finally, a solution is obtained. After the addition of the corresponding alcohol or glycol ether or polyglycol ether the reactor is flushed with nitrogen gas for 5 min to remove hydrogen chloride having formed during the reaction. After flushing with nitrogen gas the reactor is connected to the pressure release valve and ammonia gas is passed into the reactor (500 mL/min; 0.55 bar). The reaction process is controlled via a mass flow controller. Supply of ammonia gas is finished as soon as the ammonia gas flow decreases to 0 mL/ min. The pressure is released and the reactor is flushed purged with nitrogen gas to remove residual ammonia gas. Subsequently, the reaction mixture is filtered over a glass frit (D4). By a subsequent filtration over Celite® colloidal solid residues are separated. Finally, the solvent is removed under reduced pressure (10.sup.-2 mbar, up to 60° C.) and the desired product [W(O)(OR).sub.4] is obtained as solid or liquid.

Example 7 to 10: Analytical Data

[0313] Example 7: WO(OR)4 with R =

[00002]$i\text{Pr;}$

8.0 eq

[00003]$i\text{PrOH};$

colorless solid, 81% yield

[0314] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.30 (d, 24 H), 4.79-4.95 (m, 4 H); trace metals analysis (lCP-OES): all trace metals <10 ppm; silicon (Si) content (ICP-OES): < 10 ppm.

Example 8: WO(OR).SUB.4 With R = sBu; 8.0 eq sBuOH; Yellow Liquid, 83% Yield

[0315] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 0.95 (t, 12 H), 1.29 (dd, 12 H), 1.53-1.69 (m, 8 H), 4.60-4.69 (m, 4 H); trace metals analysis (lCP-OES): all trace metals <10 ppm; silicon (Si) content (lCP-OES): < 10 ppm.

Example 9: WO(OR).SUB.4 With R = C_{3.H.SUB.6.OCH.SUB.3.; 4.0 eq CH.SUB.3.OC.SUB.3.H.SUB.6.OH; Yellow Liquid, 87% Yield}

[0316] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.23-1.27 (m, 12 H, CHCH3) 3.38-3.43 (m, 20 H, OCH2+OCH3), 4.74-4.83 (m, 4 H, CH); elemental analysis: tungsten (W) content = 32.8%; trace metals analysis (lCP-OES): all trace metals <10 ppm silicon (Si) content (lCP-OES): < 10 ppm; chlorine (Cl) content < 250 ppm;

Example 10: WO(OR).SUB.4 With R = C_{3.H.SUB.6.OC.SUB.3.H.SUB.6.OC.SUB.3.H.SUB.7.; 4.0 eq C.SUB.3.H.SUB.7.OC.SUB.3.H.SUB.6.OC.SUB.3.H.SUB.6.OH; Red-Orange Liquid, 86% Yield}

[0317] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 0.85 - 0.97 (m, 3 H) 1.08 - 1.40 (m, 7 H), 1.58 (t, J=7.08 Hz, 2 H), 3.30 - 4.05 (m, 7 H), 4.24 - 4.61 (m, 1 H), 4.67 - 4.93 (m, 1 H); elemental analysis: tungsten (W) content = 20.1%; trace metals analysis (ICP-OES): all trace metals <10 ppm, silicon (Si) content (lCP-OES): < 10 ppm, chlorine (Cl) content < 250 ppm.

Synthesis of [W(O)(OR).SUB.4.] With Et.SUB.2.NH Starting From WCl.SUB.6

Example 11: Preparation of [WO(OC.SUB.3.H.SUB.6.OCH.SUB.3.).SUB.4.]

[0318] The reactor was dried under vacuum at 60° C. for 1 hour. Heptane and 1-methoxy-2-propanol were dried over molecular sieve for several days according to standard methods.

[0319] Under inert gas atmosphere 100 g tungsten(VI) chloride (252.15 mmol; 1.0 eq.) are dosed into a 1 L stirred reactor by a solid substances metering funnel. Subsequently, tungsten(VI) chloride is suspended and partly dissolved, respectively, in 500 mL heptane (anhydrous) and the reaction mixture is stirred at ambient temperature. 14.66 g acetone (252.15 mmol, 1.0 eq.) in 200 mL heptane are added over a period of about 1 h. The reaction mixture is stirred for 16 h at ambient temperature, whereby a bright orange reaction mixture is obtained. To the WOCl.sub.4 slurry stirred at about 20° C. the 1-methoxy-2-propanol (1.01 mol, 4.0 eq) is added slowly over a period of about 1 h. During the addition of 1-methoxy-2-propanol the precipitate is slowly dissolved and the color of the reaction mixture changes to yellow. Finally, a solution is obtained. After the addition of 1-methoxy-2-propanol the reactor is flushed with nitrogen gas for 5 min to remove hydrogen chloride having formed during the reaction. After flushing with nitrogen gas, 74.57 g Et.sub.2NH (1.02 mol, 4.04 eq) are added via dropping funnel over a period of 1 h, at 20° C. to the reaction solution. After complete addition of the Et.sub.2NH the colorless reaction mixture is stirred for another 1 h at room temperature. Subsequently, the reaction mixture is filtered over a glass frit (D4). By a subsequent filtration over Celite® colloidal solid residues are separated. Finally, the solvent is removed under reduced pressure (10.sup.-2 mbar, up to 60° C.) and the desired product [W(O)(OC.sub.3H.sub.6OCH.sub.3).sub.4] is obtained as yellow liquid (84%).

[0320] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.19-1.23 (t, 12 H, CHCH3), 3.35-3.40 (m, 20 H, OCH2+OCH3), 4.69-4.78 (m, 4 H, CH); trace metals analysis (lCP-OES): all trace metals <10 ppm; silicon (Si) content (lCP-OES): < 10 ppm

Synthesis of [W(O)(OR).SUB.4.] With Different Amine Bases, Starting From WOCl.SUB.4 Synthesized According to Example 2

Example 12 to 19

[0321] A flask was charged with tungsten oxytetrachloride (3.00 g, 8.78 mmol, 1.00 eq) and suspended/ dissolved in 125 mL of anhydrous heptane. The reaction mixture was cooled with stirring to 0° C. To this stirred solution 6.35 g 1-methoxy-2-propanol (70.5 mmol, 8.00 eq) were added. To this reaction solution 4.00 eq corresponding base were added, whereas a colorless solid was formed. The reaction mixture was warmed to room temperature and the solids removed via filtration over Celite®. After removal of all volatile side products and components the product was obtained as slightly yellow liquid.

Example 12 to 19: Analytical Data

Example 12: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = Methylamine; Yellow Liquid; 67% Yield

[0322] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.20-1.24 (m, 12H, CHCH3), 3.35-3.41 (m, 20H, OCH2+OCH3), 4.71-4.79 (m, 4H, CH).

Example 13: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = Triethylamine; Yellow Liquid; 83% Yield

[0323] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.19-1.23 (m, 12H, CHCH3), 3.34-3.40 (m, 20H, OCH2+OCH3), 4.68-4.82 (m, 4H, CH).

Example 14: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = 1,2-ethylene Diamine; Yellow Liquid; 93% Yield

[0324] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.17-1.19 (m, 12H, CHCH3), 3.30-3.40 (m, 20H, OCH2+OCH3), 4.68-4.73 (m, 4H, CH).

Example 15: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = N,N,N′,N′-tetramethylethylene Diamine; Yellow Liquid; 30% Yield

[0325] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.24-1.28 (m, 12H, CHCH3), 3.37-3.47 (m, 20H, OCH2+OCH3), 4.74-4.84 (m, 4H, CH).

Example 16: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU); Yellow Liquid; 25% Yield

[0326] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.29-1.33 (m, 12H, CHCH3), 3.36-3.45 (m, 20H, OCH2+OCH3), 4.97-5.05 (m, 4H, CH).

Example 17: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = Morpholine; Yellow Liquid; 19% Yield

[0327] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.29-1.33 (m, 12H, CHCH3), 3.40-3.45 (m, 20H, OCH2+OCH3), 4.76-4.85 (m, 4H, CH).

Example 18: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = Pyridine; Yellow Liquid; 80% Yield

[0328] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.24-1.28 (m, 12H, CHCH3), 3.38-3.43 (m, 20H, OCH2+OCH3), 4.74-4.84 (m, 4H, CH).

Example 19: WO(OC.SUB.3.HeOCH.SUB.3.).SUB.4 With Base = Imidazole; Yellow Liquid; 77% Yield

[0329] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K) δ (ppm) = 1.22-1.26 (m, 12H, CHCH3), 3.36-3.46 (m, 20H, OCH2+OCH3), 4.73-4.83 (m, 4H, CH).

Synthesis of [W(O)(OR).SUB.4.] With WOCl.SUB.4 Synthesized According to Example 2

Example 20: Preparation of W(O)(OC.SUB.3.H.SUB.6.OCH.SUB.3.).SUB.4

[0330] The reactor is dried under vacuum at 60° C. for 1 hour. Heptane and the glycol ether 1-methoxy-2-propanol are dried over molecular sieve for several days according to standard methods.

[0331] Under inert gas atmosphere a 1 L stirred reactor is charged with 1.0 eq. tungsten(VI) oxy tetrachloride (252.15 mmol) by a solid substances metering funnel. Subsequently, tungsten(VI) oxy tetrachloride is suspended and partly dissolved, respectively, in 500 mL heptane (anhydrous) and the reaction mixture is stirred at ambient temperature. To the tungsten(VI) oxy tetrachloride slurry stirred at about 20° C. 1-methoxy-2-propanol (1.01 mol; 4.0 eq.) are added slowly over a period of about 1 h. After the addition of 1-methoxy-2-propanol the reactor is flushed with nitrogen gas for 5 min to remove hydrogen chloride having formed during the reaction. After flushing with nitrogen gas the reactor is connected to the pressure release valve and ammonia gas is passed into the reactor (500 mL/min; 0.55 bar). The reaction process is controlled via a mass flow controller. Supply of ammonia gas is finished as soon as the ammonia gas flow decreases to 0 mL/ min. The pressure is released and the reactor is flushed purged with nitrogen gas to remove residual ammonia gas. Subsequently, the reaction mixture is filtered over a glass frit (D4). By a subsequent filtration over Celite® colloidal solid residues are separated. Finally, the solvent is removed under reduced pressure (10.sup.-2 mbar, up to 60° C.) and the desired product [W(O)(OC.sub.3H.sub.6OCH.sub.3).sub.4] (>80%) is obtained as yellow liquid.

[0332] From the results of successful one-pot synthesis according to Example 9 the conclusion is made that a synthesis, starting from isolated, essentially silicon-free WOel.sub.4 does result in essentially silicon-free [WO(OR).sub.4] that is obtained analogous to Example 9. The reasons for this are as follows:

[0333] It has been proven herein that essentially silicon-free WOCl.sub.4 with a silicon content of less than 1.500 ppb is obtained according to the process herein described (cf. Examples 1 to 6). When reaction of WOCl.sub.4 with an alcohol ROH and essentially silicon-free base is carried out, then no further impurities by a silicon species can be introduced. Thus, a silicon content of < 1.500 ppb cannot be exceeded by the end-product of the synthesis according to Example 12. Yields and purities achieved by this Example are similar or identical to those obtained from the one-pot synthesis herein described.

[0334] In addition to the above mentioned reaction and according to Example 12, the following

Examples 21

[0335] Based on Examples 7 to 11, the results of the following Examples can be obtained when varying the alcohol and the silicon-free based are varied.

[0336] Abbreviations: Yd.= Yield; Ex. No.: Example Number;

[0337] Bases used: MA= Methylamine, DA= Diethylamine, TA= Triethylamine, 12E=1,2-Ethylenediamine, TMEDA= N,N,N,N′,N′-Tetramethylethane-1,2-diamine (TMEDA), DBU=1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU), Mo=Morpholine, Py=Pyridine, lm=lmidazole, DMAP=N,N-Dimethylaminopyridine, NH3=Ammonia

TABLE-US-00001 Ex. No. Alcohol Base Yd. [%] T M D E D M N M D T 12 D B M A H A A A E A U o Py lm P 3 MeOH X 83 X 96 X 86 X 97 X 52 X 38 X 25 X 83 X 88 X 91 X 95 Ethanol X 82 X 97 X 80 X 93 X 58 X 33 X 20 X 88 X 81 X 93 X 94 Propan-1-ol X 84 X 90 X 88 X 90 X 56 X 38 X 21 X 85 X 83 X 95 X 90 X 85 Propan-2-ol X 91 X 81 X 98 X 54 X 32 X 27 X 86 X 89 X 91 X 95 2-Methylpropan-1-ol X 89 X 90 X 87 X 93 X 50 X 36 X 23 X 82 X 87 X 93 X 91 2-Methylpropan-2-ol X 88 X 98 X 89 X 95 X 57 X 30 X 22 X 84 X 85 X 95 X 96 Butan-1-ol X 86 X 90 X 82 X 96 X 55 X 34 X 23 X 81 X 86 X 90 X 92 Butan-2-ol X 87 X 95 X 84 X 92 X 58 X 37 X 24 X 83 X 85 X 94 X 95 2-Methylbutan-1-ol X 81 X 94 X 83 X 91 X 52 X 34 X 28 X 85 X 88 X 90 X 94 3-Methylbutan-1-ol X 83 X 92 X 85 X 94 X 51 X 31 X 26 X 82 X 80 X 96 X 92 2-Methylbutan-2-ol X 80 X 93 X 83 X 94 X 59 X 39 X 29 X 89 X 80 X 97 X 97 3-Methylbutan-2-ol X 80 X 96 X 83 X 94 X 59 X 34 X 29 X 83 X 85 X 94 X 97 Pentan-1-ol X 83 X 97 X 86 X 95 X 52 X 37 X 25 X 88 X 80 X 96 X 92 Pentan-2-ol X 82 X 90 X 80 X 97 X 51 X 34 X 20 X 85 X 88 X 97 X 94 Pentan-3-ol X 84 X 91 X 88 X 93 X 52 X 31 X 21 X 86 X 81 X 90 X 95 2,2-Dimethylpropan-1-ol X 85 X 90 X 81 X 90 X 58 X 39 X 27 X 82 X 83 X 95 X 94 Hexan-1-ol X 89 X 98 X 87 X 98 X 56 X 38 X 23 X 84 X 89 X 93 X 90 Hexan-2-ol X 88 X 90 X 89 X 93 X 54 X 33 X 22 X 81 X 87 X 90 X 95 Hexan-3-ol X 86 X 95 X 82 X 95 X 50 X 38 X 23 X 83 X 85 X 91 X 91 2-Methylpentan-1-ol X 87 X 94 X 84 X 96 X 57 X 32 X 24 X 85 X 86 X 93 X 96 3-Methylpentan-1-ol X 81 X 92 X 83 X 92 X 55 X 36 X 28 X 82 X 85 X 95 X 92 4-Methylpentan-1-ol X 83 X 90 X 85 X 91 X 58 X 30 X 26 X 89 X 88 X 91 X 95 2-Methylpentan-2-ol X 85 X 97 X 83 X 94 X 58 X 30 X 26 X 83 X 80 X 94 X 96 3-Methylpentan-2-ol X 80 X 92 X 88 X 96 X 55 X 34 X 29 X 86 X 83 X 95 X 97 4-Methylpentan-2-ol X 88 X 94 X 85 X 97 X 57 X 37 X 25 X 80 X 82 X 97 X 90 2-Methylpentan-3-ol X 81 X 95 X 86 X 90 X 50 X 34 X 20 X 88 X 84 X 93 X 91 3-Methylpentan-3-ol X 83 X 94 X 82 X 95 X 54 X 31 X 21 X 81 X 85 X 90 X 90 2,2-Dimethylbutan-1-ol X 80 X 89 X 90 X 84 X 93 X 50 X 39 X 27 X 87 X 89 X 98 2,3-Dimethylbutan-1-ol X 87 X 95 X 81 X 90 X 56 X 38 X 23 X 89 X 88 X 93 X 90 3,3-Dimethylbutan-1-ol X 85 X 91 X 83 X 91 X 58 X 33 X 22 X 82 X 86 X 95 X 95 2,3-Dimethylbutan-2-ol X 86 X 96 X 85 X 93 X 53 X 38 X 23 X 84 X 87 X 96 X 94 3,3-Dimethylbutan-2-ol X 85 X 92 X 82 X 95 X 55 X 32 X 24 X 83 X 81 X 92 X 92 X 88 2-Methyl-2-propanol X 95 X 89 X 91 X 52 X 36 X 28 X 85 X 83 X 91 X 90 2-Methyl-2-propanol X 88 X 95 X 89 X 93 X 55 X 36 X 28 X 88 X 87 X 91 X 95 2-Methyl-2-propanol X 85 X 92 X 85 X 90 X 52 X 38 X 26 X 81 X 81 X 94 X 92 2-Methyl-2-propanol X 80 X 96 X 82 X 91 X 53 X 33 X 29 X 87 X 83 X 95 X 94 2-Methyl-2-propanol X 88 X 97 X 83 X 93 X 58 X 32 X 25 X 89 X 80 X 97 X 96 2-Methyl-2-propanol X 81 X 92 X 83 X 95 X 55 X 30 X 20 X 82 X 83 X 93 X 97 2-Methyl-2-propanol X 83 X 94 X 88 X 91 X 57 X 34 X 21 X 84 X 82 X 90 X 90 2-Methyl-2-propanol X 89 X 95 X 85 X 94 X 50 X 37 X 27 X 83 X 84 X 98 X 91 2-Methyl-2-propanol X 87 X 94 X 86 X 96 X 54 X 34 X 23 X 85 X 85 X 93 X 90 2-Methyl-2-propanol X 85 X 90 X 82 X 97 X 50 X 31 X 22 X 83 X 89 X 95 X 98 2-Methyl-2-propanol X 86 X 95 X 84 X 90 X 56 X 39 X 23 X 86 X 88 X 96 X 90 2-Methyl-2-propanol X 85 X 91 X 81 X 95 X 58 X 38 X 24 X 80 X 86 X 92 X 95 2-Methyl-2-propanol X 87 X 90 X 87 X 95 X 50 X 37 X 24 X 89 X 88 X 93 X 91 2-Methyl-2-propanol X 81 X 98 X 85 X 92 X 54 X 34 X 23 X 85 X 81 X 90 X 94 3,3-Dimethylbutan-2-ol X 83 X 95 X 88 X 96 X 50 X 31 X 28 X 82 X 87 X 91 X 95 2-Ethylbutan-1-ol X 80 X 90 X 80 X 90 X 50 X 30 X 20 X 80 X 80 X 90 X 90 Cyclohexanol X 80 X 90 X 85 X 97 X 56 X 39 X 26 X 83 X 89 X 93 X 97 Heptan-1-ol X 83 X 95 X 88 X 92 X 58 X 38 X 29 X 83 X 82 X 95 X 93 Heptan-2-ol X 80 X 90 X 80 X 90 X 50 X 30 X 20 X 80 X 80 X 90 X 90 Heptan-3-ol X 82 X 92 X 85 X 94 X 55 X 36 X 25 X 88 X 84 X 91 X 90 1,1,1,3,3,3-Hexafluoro-propan-2-ol X 84 X 94 X 80 X 95 X 52 X 38 X 20 X 85 X 83 X 94 X 98 X 85 X 96 1,1,1,3,3,3-Hexafluoro-2—(trifluoromethyl)-propan-2-ol X 88 X 94 X 53 X 33 X 21 X 86 X 85 X 96 X 93 2-Fluoroethanol X 85 X 96 X 88 X 94 X 53 X 33 X 21 X 86 X 85 X 96 X 93 3-Fluoropropan-1-ol X 89 X 97 X 81 X 90 X 58 X 32 X 27 X 82 X 83 X 97 X 95 4-Fluoro-1-butanol X 88 X 90 X 83 X 95 X 55 X 30 X 23 X 84 X 86 X 90 X 96 (2,2-Dichloro-3,3-dimethylcyclopropyl)m ethanol X 86 X 91 X 89 X 91 X 57 X 34 X 22 X 81 X 80 X 95 X 92 (2,2-Dichloro-1-phenylcyclopropyl)met hanol X 84 X 89 X 81 X 91 X 56 X 38 X 29 X 86 X 83 X 94 X 93 1,1,5-Trihydroperfluorpentan ol X 85 X 95 X 83 X 95 X 58 X 33 X 25 X 82 X 86 X 96 X 89 6-Chloro-1-hexanol X 89 X 92 X 89 X 92 X 55 X 32 X 20 X 84 X 80 X 97 X 98 X 88 6-Bromo-1-hexanol X 94 X 87 X 96 X 52 X 30 X 21 X 81 X 88 X 89 X 93 8-Chloro-1-octanol X 86 X 96 X 85 X 97 X 53 X 34 X 27 X 85 X 81 X 95 X 95 8-Bromo-1-octanol X 87 X 97 X 88 X 92 X 58 X 37 X 23 X 82 X 87 X 93 X 96 2-Methyl-2-propanol X 81 X 89 X 85 X 94 X 55 X 34 X 22 X 83 X 89 X 89 X 92 10-Chloro-1-decanol X 83 X 91 X 88 X 95 X 57 X 31 X 24 X 83 X 82 X 91 X 91 10-Bromo-1-decanol X 80 X 89 X 85 X 94 X 50 X 39 X 23 X 88 X 84 X 93 X 94 4-Trifluoromethan-cyclohexan-1-ol X 83 X 98 X 80 X 89 X 54 X 38 X 28 X 85 X 83 X 95 X 95 Ethylene glycol monomethyl ether X 82 X 95 X 88 X 95 X 50 X 36 X 26 X 89 X 85 X 91 X 97 Ethylene glycol ethyl ether X 83 X 93 X 84 X 90 X 57 X 40 X 22 X 81 X 86 X 91 X 94 Ethylene glycol monopropyl ether X 86 X 90 X 85 X 95 X 59 X 38 X 24 X 83 X 82 X 95 X 96 Ethylene glycol monoisopropyl ether X 80 X 98 X 89 X 92 X 54 X 35 X 23 X 89 X 84 X 92 X 97 Ethylene glycol monobutyl ether X 88 X 93 X 88 X 94 X 50 X 38 X 28 X 87 X 81 X 96 X 90 Ethylene glycol monopentyl ether X 80 X 90 X 80 X 90 X 50 X 30 X 20 X 80 X 80 X 90 X 90 Ethylene glycol monohexyl ether X 81 X 95 X 86 X 96 X 56 X 33 X 26 X 85 X 85 X 97 X 95 ethylene glycol monobenzyl ether X 87 X 96 X 87 X 97 X 58 X 32 X 30 X 88 X 82 X 92 X 93 diethylene glycol monomethyl ether X 89 X 92 X 81 X 90 X 55 X 30 X 25 X 85 X 83 X 94 X 90 diethylene glycol monoethyl ether X 82 X 91 X 83 X 91 X 52 X 34 X 20 X 88 X 83 X 95 X 91 diethylene glycol monopropyl ether X 84 X 94 X 80 X 95 X 53 X 37 X 21 X 85 X 88 X 94 X 93 diethylene glycol monoisopropyl ether X 83 X 95 X 83 X 98 X 58 X 34 X 27 X 80 X 85 X 90 X 95 diethylene glycol monobutyl ether X 85 X 97 X 82 X 95 X 55 X 31 X 23 X 88 X 89 X 95 X 91 diethylene glycol monopentyl ether X 88 X 94 X 86 X 91 X 55 X 39 X 22 X 85 X 86 X 95 X 95 X 81 X 95 diethylene glycol monohexyl ether X 87 X 95 X 50 X 38 X 24 X 88 X 82 X 94 X 93 diethylene glycol monophenyl ether X 87 X 97 X 81 X 98 X 54 X 35 X 23 X 85 X 83 X 90 X 90 diethylene glycol monobenzyl ether X 89 X 93 X 83 X 95 X 50 X 38 X 28 X 80 X 83 X 95 X 91 propylene glycol monoethyl ether X 82 X 90 X 80 X 90 X 56 X 33 X 26 X 88 X 88 X 91 X 93 propylene glycol monopropyl ether X 84 X 97 X 83 X 95 X 58 X 32 X 29 X 81 X 85 X 95 X 95 propylene glycol monoisopropyl ether X 83 X 93 X 82 X 92 X 55 X 30 X 25 X 83 X 89 X 92 X 91 propylene glycol monobutyl ether X 85 X 95 X 84 X 94 X 52 X 34 X 19 X 89 X 82 X 96 X 94 propylene glycol monopentyl ether X 83 X 96 X 85 X 96 X 53 X 35 X 21 X 87 X 84 X 97 X 96 X 86 propylene glycol monohexyl ether X 92 X 89 X 97 X 58 X 34 X 25 X 85 X 81 X 92 X 97 propylene glycol monophenyl ether X 80 X 91 X 88 X 90 X 55 X 31 X 23 X 88 X 85 X 94 X 90 propylene glycol monobenzyl ether X 83 X 96 X 86 X 92 X 55 X 35 X 20 X 81 X 85 X 97 X 94 iso-propylene glycol monomethyl ether X 86 X 92 X 87 X 94 X 52 X 34 X 21 X 83 X 84 X 92 X 93 iso-propylene glycol monoethyl ether X 80 X 91 X 81 X 96 X 53 X 31 X 25 X 89 X 81 X 94 X 89 iso-propylene glycol monopropyl ether X 88 X 94 X 83 X 97 X 58 X 39 X 23 X 87 X 85 X 95 X 91 iso-propylene glycol monoisopropyl ether X 81 X 95 X 80 X 89 X 55 X 38 X 22 X 85 X 86 X 94 X 93 iso-propylene glycol monobutyl ether X 87 X 97 X 83 X 91 X 55 X 35 X 24 X 88 X 82 X 90 X 95 iso-propylene glycol monopentyl ether X 89 X 93 X 82 X 95 X 50 X 38 X 23 X 85 X 83 X 95 X 91 iso-propylene glycol monohexyl ether X 82 X 90 X 84 X 98 X 54 X 33 X 28 X 88 X 83 X 91 X 94 iso-propylene glycol monophenyl ether X 84 X 97 X 85 X 95 X 50 X 32 X 26 X 85 X 88 X 95 X 96 dipropylene glycol monopropyl ether X 83 X 93 X 89 X 90 X 56 X 30 X 29 X 80 X 85 X 92 X 97 iso-propylene glycol monobenzyl ether X 85 X 95 X 88 X 95 X 58 X 34 X 25 X 88 X 89 X 96 X 90 dipropylene glycol monomethyl ether X 85 X 94 X 83 X 96 X 58 X 32 X 25 X 86 X 81 X 92 X 97 1-methoxy-2-propanol X 84 X 93 X 86 X 92 X 55 X 34 X 20 X 87 X 83 X 94 X 92 tripropylene glycol monomethyl ether X 81 X 89 X 80 X 91 X 52 X 30 X 21 X 81 X 89 X 96 X 94 dipropylene glycol monobutyl ether X 85 X 91 X 88 X 94 X 53 X 35 X 25 X 83 X 87 X 97 X 95 1-butoxy-2-propanol X 86 X 93 X 81 X 95 X 58 X 34 X 23 X 80 X 85 X 90 X 94 tripropylene glycol monobutyl ether X 82 X 95 X 87 X 97 X 55 X 31 X 22 X 83 X 88 X 91 X 95 1-propoxy-2-propanol X 83 X 91 X 89 X 93 X 55 X 39 X 24 X 82 X 85 X 95 X 95 1-methoxy-1-ethanol X 83 X 94 X 82 X 90 X 50 X 38 X 23 X 84 X 88 X 98 X 91 1-Ethoxy-2-ethanol X 88 X 96 X 84 X 97 X 54 X 35 X 28 X 85 X 85 X 95 X 95 1-Propoxy-2-ethanol X 85 X 97 X 83 X 93 X 50 X 38 X 26 X 89 X 80 X 90 X 92 1-Butoxy-2-ethanol X 89 X 90 X 85 X 95 X 56 X 33 X 29 X 88 X 88 X 95 X 96 1-Ethoxy-3-propanol X 89 X 95 X 85 X 90 X 56 X 31 X 30 X 82 X 88 X 91 X 96 1-Propoxy-3-propanol X 85 X 91 X 83 X 97 X 58 X 39 X 25 X 84 X 81 X 95 X 97 1-Methoxy-4-butanol X 84 X 84 X 86 X 93 X 55 X 38 X 20 X 85 X 83 X 98 X 92 1-Ethoxy-4-butanol X 81 X 96 X 80 X 95 X 52 X 35 X 21 X 89 X 89 X 95 X 94 1-Propoxy-4-butanol X 85 X 97 X 88 X 96 X 53 X 38 X 25 X 88 X 87 X 90 X 95 X 86 1-Butoxy-4-butanol X 90 X 81 X 92 X 58 X 33 X 23 X 86 X 85 X 95 X 94 1-Methoxy-5-pentanol X 82 X 94 X 87 X 91 X 55 X 32 X 22 X 87 X 88 X 92 X 95 1-Ethoxy-5-pentanol X 83 X 93 X 89 X 94 X 55 X 34 X 24 X 81 X 85 X 94 X 95 1-Propoxy-5-pentanol X 83 X 89 X 82 X 95 X 50 X 30 X 23 X 83 X 88 X 96 X 91

[0338] The invention is not limited to any one of the embodiments described above, but modifiable in various ways.

[0339] All features and advantages arising from the claims and the description, including design details, spatial arrangements and procedure steps, can be essential to the invention, either individually or in various combinations.

[0340] As can be seen the invention concerns a process for preparing an essentially silicon (Si) free compounds of the general formula [M(O)(OR).sub.y], wherein M = Mo, y = 3 or M = W, y = 3 or 4. Furthermore, it is directed towards compounds obtained by the aforementioned process, towards the use of such a compound obtained by the aforementioned process and a substrate having a layer of M or a layer comprising M on its surface obtained by the aforementioned process. Another objective of the herein described invention are essentially silicon free compounds obtained by the aforementioned process, of the general formula MOX.sub.y or [MOX.sub.y(solv).sub.p], wherein M = Mo, y = 3 or M = W, y = 3 or 4, X = Cl or Br, solv = an oxidizing agent Z binding or coordinating to M via at least one donor atom, p = 1 or 2. The invention is also directed towards the use of essentially silicon free compounds obtained by the aforementioned process, of the general formula MOX.sub.y or [MOX.sub.y(solv).sub.p].