Organometallic compounds and methods for preparing same

Abstract

The present disclosure provides a method for producing bis(monoalkyl-substituted cyclopentadiene)tungsten hydride compounds, such as bis(isopropylcyclopentadienyl)tungsten dihydride, via the corresponding magnesium compound and tungsten hexachloride, followed by treatment with a hydride reagent. Also provided is a method for producing bis(monoalkyl-substituted cyclopentadiene)metal halide compounds. This latter aspect is achieved by reaction of the corresponding magnesium compound with a metal halide. Representative metals used in this process include hafnium, zirconium, titanium, tantalum, niobium, tungsten, and molybdenum.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] This disclosure relates generally to methods for preparing monoalkylcyclopentadiene compounds coordinated to various metals. [Background technology]

[0002]

[0002] Many organometallic compounds are used in the fabrication of microelectronic devices. For example, US 2018 / 0166276 A describes the use of various metal precursors to deposit mask layers containing one or more metals, such as tungsten, tantalum, zirconium, hafnium, molybdenum, niobium, ruthenium, osmium, rhenium, and iridium. In particular, bis(isopropylcyclopentadienyl)tungsten dihydride (CAS No. 64561-25-7) is cited as being useful for atomic layer deposition of such mask layers.

[0003] One inherent difficulty in working with cyclopentadiene is its tendency to dimerize via the Diels-Alder reaction. This dimerization proceeds over several hours at room temperature but can be reversed by heating, sometimes requiring a cracking step. Furthermore, alkylation reactions utilizing cyclopentadiene anion species can result in the formation of di- and tri-alkyl species, which further complicate the synthetic regime by reducing yields and requiring further separation and purification.

[0004]

[0004] Therefore, improved methodologies for preparing such compounds are desirable. Summary of the Invention

[0005] Generally, the present disclosure provides a method for producing bis(monoalkyl-substituted cyclopentadiene)tungsten hydride compounds, such as bis(isopropylcyclopentadienyl)tungsten dihydride, via the corresponding magnesium compound and tungsten hexachloride, followed by treatment with a hydride reagent. Bis(isopropylcyclopentadienyl)tungsten dihydride (CAS No. 64561-25-7) is useful for atomic layer deposition (see, e.g., US 2018 / 0166276 A).

[0006] In another aspect, the present disclosure provides a method for producing bis(monoalkyl-substituted cyclopentadiene) metal halide compounds. This latter aspect is achieved by reacting the corresponding magnesium compound with a metal halide. Exemplary metals used in this process include hafnium, zirconium, titanium, tantalum, niobium, and molybdenum. DETAILED DESCRIPTION OF THE INVENTION

[0006]

[0007] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0007]

[0008] The term "about" generally refers to a range of numbers considered equivalent to a stated value (e.g., having the same function or result). In many instances, the term "about" may include numbers that are rounded to the nearest significant figure.

[0008]

[0009] Numeric ranges expressed using endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0009]

[0010] In a first aspect, the present disclosure provides a compound of formula (I): TIFF0007733242000001.tif77170[where, R 1 and R 1 are independently selected from hydrogen and C1-C8 alkyl, formula, TIFF0007733242000002.tif80170 with WCl6, followed by treatment with (e.g., addition of) a hydride reagent.

[0010]

[0011] In the above method, suitable hydride reagents include, but are not limited to, NaBH, LiBH, LiAlH, LiBH(CHCH), [(isobutyl)AlBH], NaBHCN, Na[HB(OC(O)CH)], BH-tetrahydrofuran, BH-S(CH), diisobutylaluminum hydride (also known as DIBAL), and sodium bis(2-methoxyethoxy)aluminum hydride (NaAlH(OCHCHOCH)). In one embodiment, the hydride reagent is NaBH.

[0011]

[0012] Thus, the disclosed method provides a facile methodology for preparing bis(monoalkyl)cyclopentadiene tungsten compounds useful as tungsten-containing precursors in the preparation of tungsten oxide and sulfide films by atomic layer deposition. In one embodiment, R and R 1 is methyl, i.e., the monoalkyl substituent on the cyclopentadiene ring is isopropyl. In other embodiments, R and R 1 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, and sec-octyl.

[0012]

[0013] The above bis(monoalkyl-substituted cyclopentadiene) magnesium compounds can be prepared by reacting the corresponding fulvene compound with a dialkyl magnesium compound. Thus, in another aspect, the present disclosure provides a compound represented by formula (I): TIFF0007733242000003.tif77170[where, R 1 and R 1 is independently selected from hydrogen and C1-C8 alkyl, the method comprising: formula, TIFF0007733242000004.tif29170 with a dialkyl magnesium compound to form a compound of formula: TIFF0007733242000005.tif74170, followed by treatment (e.g., addition) with a compound of formula WCl6, followed by treatment (e.g., addition) with a hydride reagent.

[0013] In this method, suitable dialkylmagnesium compounds include compounds having alkyl groups capable of β-hydride elimination, examples include Mg(C-C alkyl), Mg(C-C alkyl), or Mg(C-C alkyl). In one embodiment, the dialkylmagnesium compound is selected from Mg(CHCHCHCHCH) or Mg[(CH)(CH)(CHCH)][CHCHCHCHCH].

[0014]

[0015] formula, The fulvene starting material in TIFF0007733242000006.tif27170 has the corresponding formula R 1 -C(O)-R 2 with cyclopentadiene in the presence of a base such as pyrrolidone or an alkali metal hydroxide.

[0015] As noted above, compounds of formula (I) are useful as precursors in atomic layer deposition on microelectronic device substrates. See, for example, US 2018 / 0166276 A, particularly bis(isopropylcyclopentadienyl)tungsten dihydride (CAS No. 64561-25-7). Advantageously, compounds of formula (I) are thus provided substantially free of undesirable contaminants, such as lithium and bis(alkylated)metallocenes.

[0016] In a further aspect, the present disclosure provides a compound of formula (II): TIFF0007733242000007.tif84170 [wherein M is selected from Hf, Zr, Ti, Ta, Nb, W, and Mo; [In the formula, R 1 and R 1 is independently selected from hydrogen and C1-C8 alkyl, the method comprising: formula, TIFF0007733242000008.tif83170 with a compound of formula MX4, wherein X is selected from chloro, bromo, and iodo.

[0017]

[0017] In this embodiment, the above bis(monoalkylcyclopentadiene) magnesium compound can be used as a starting material to prepare various organometallic compounds of formula (II) by subsequent reaction with the corresponding metal tetrahalide, e.g., HfCl4. Compounds of formula (II) are widely used as polyolefin catalysts, such as polyethylene and polypropylene.

[0018] In one embodiment, M is Hf, Zr, Ti, or Mo.

[0019] In one embodiment, R and R 1 is methyl, i.e., represents an isopropyl group. In another embodiment, R and R 1are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, and sec-octyl.

[0020]

[0020] In the present disclosure, processes beginning with substituted fulvene starting materials allow for the synthesis of only mono-alkyl-substituted compounds of formulas (I) and (II), as opposed to the formation of multiply alkylated cyclopentadienyl species that can occur in conventional alkylation reaction approaches. The products can be deprotonated with an initial metal-Cp complex (i.e., anionic cyclopentadiene) prior to secondary alkylation, e.g., with an alkyl bromide. In the latter case, the level of multi-alkylation can range from 0.5 to 5 weight percent. Advantageously, the disclosed processes provide mono-alkylated species free of detectable levels of multiply alkylated species by gas chromatography (e.g., GC and GC-MS) or NMR. Thus, in further embodiments, the disclosed processes provide products having less than 0.5 weight percent, less than 0.3 weight percent, or less than 0.1 weight percent multiply alkylated species as measured by gas chromatography.

[0021] Furthermore, in view of the substituted fulvene approach outlined herein, the present disclosure further advantageously provides products of formulas (I) and (II) that are devoid of dicyclopentadiene and mixed dicyclopentadiene species.

[0022] Example -

[0023] ( i PrCp)2Mg ( i Synthesis procedure for PrCp)2WH2 Under inert conditions, WCl6 (2.00 g, 5 mmol) was charged into a 250 mL Schlenk flask containing a magnetic material. Hexane (10 mL) and DME (20 mL) were added to the flask, and the reaction mixture was cooled to 0-5 °C with stirring.i PrCp)2Mg (2.41 g, 10 mmol) was added, and the resulting mixture was stirred for 30 minutes. THF (20 mL) was charged while maintaining a temperature of 0-5°C. NaBH4 (0.51 g, 13.4 mmol) was added under nitrogen, resulting in a slight exotherm (+3°C). The reaction mixture changed from brown to pale yellow. The reaction mixture was allowed to warm slowly to room temperature over 1.5 hours. The reaction mixture turned pale yellow. The reaction mixture was heated to 50-55°C for 2 hours and then cooled to approximately 30°C. All solvent was removed under vacuum. Hexane (50 mL) was added to the flask, and the mixture was cooled to 0°C. DI water (50 mL) was added slowly with stirring, resulting in a +2°C exotherm. After stirring for 15 minutes, the aqueous layer was discarded. The reaction flask was cooled to 0°C, and 30% aqueous acetic acid (20 mL) was added with stirring. After stirring for 15 minutes, the aqueous layer was separated, and the organic layer was discarded. Hexane (50 mL) was added to the aqueous layer and cooled to 0° C. The aqueous layer was neutralized with 50% NaOH solution. The organic layer was separated and all volatiles were removed in vacuo to give 1.8 g of a brown viscous liquid in 83% yield. The NMR data are as follows: 1 H-NMR (C6D6, δ-ppm): 4.18 (d, 4H, CpH), 2.42 (m, 2H, CH(CH3)2), 1.1 (d, 6H, CH(CH3)2), and -11.85 (s, 2H, WH).

[0023]

[0024] Aspects

[0025] In a first aspect, the present disclosure provides a compound of formula (I): TIFF0007733242000009.tif77170[where, R 1 and R 1 is independently selected from hydrogen and C1-C8 alkyl, the method comprising: formula, The method includes contacting the compound of formula (I) with WCl6 and adding a hydride reagent.

[0024]

[0026] In a second aspect, the disclosure provides the method of the first aspect, wherein the hydride reagent is NaBH, LiAlH, LiBH, LiBH(CHCH), [(isobutyl)AlBH], NaBHCN, Na[HB(OC(O)CH)], BH-tetrahydrofuran, BH-S(CH), diisobutylaluminum hydride, or sodium bis(2-methoxyethoxy)aluminum hydride.

[0025]

[0027] In a third aspect, the present disclosure provides a method of the first or second aspect, wherein R and R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, or sec-octyl.

[0026]

[0028] In a fourth aspect, the present disclosure provides the method of the first, second, or third aspect, wherein R and R 1 is methyl.

[0027]

[0029] In a fifth aspect, the present disclosure provides the method of any one of the first to fourth aspects, wherein the hydride reagent is NaBH4.

[0028]

[0030] In a sixth aspect, the disclosure provides the method of any one of the first to fifth aspects, wherein the compound of formula (I) has less than about 0.5% by weight, less than about 0.3% by weight, or less than about 0.1% by weight of multiply alkylated species.

[0029]

[0031] In a seventh aspect, the present disclosure provides the method of any one of the first to sixth aspects, wherein the compound of formula (I) is devoid of cyclopentadiene species and mixed dicyclopentadiene species.

[0030]

[0032] In an eighth aspect, the present disclosure provides a compound of formula (I): TIFF0007733242000011.tif77170 [wherein R and R 1 are independently selected from hydrogen and C1-C8 alkyl, wherein the compound of formula (I) has less than about 0.5 weight percent of multiply alkylated species as determined by gas chromatography.

[0031]

[0033] In a ninth aspect, the present disclosure provides the compound of the eighth aspect, a compound of Formula (I) having less than about 0.3 weight percent or less than about 0.1 weight percent of multiply alkylated species as measured by gas chromatography.

[0032]

[0034] In a tenth aspect, the present disclosure provides the method of the ninth or tenth aspect, wherein the compound of formula (I) is further devoid of dicyclopentadiene species and mixed dicyclopentadiene species.

[0033]

[0035] In an eleventh aspect, the present disclosure provides a compound of formula (I): TIFF0007733242000012.tif77170[where, R 1 and R 1 is independently selected from hydrogen and C1-C8 alkyl, the method comprising: formula, TIFF0007733242000013.tif23170 with a dialkyl magnesium compound to form a compound of formula: providing the compound of formula TIFF0007733242000014.tif74170, adding WCl6, and adding a hydride reagent.

[0034]

[0036] In a twelfth aspect, the present disclosure provides the method of the eleventh aspect, wherein the hydride reagent is NaBH, LiAlH, LiBH, LiBH(CHCH), [(isobutyl)AlBH], NaBHCN, Na[HB(OC(O)CH)], BH-tetrahydrofuran, BH-S(CH), diisobutylaluminum hydride, or sodium bis(2-methoxyethoxy)aluminum hydride.

[0035]

[0037] In a thirteenth aspect, the present disclosure provides the method of any one of the eleventh to twelfth aspects, wherein the hydride reagent is NaBH4.

[0036]

[0038] In a fourteenth aspect, the present disclosure provides a method of any one of the eleventh to thirteenth aspects, wherein R and R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, or sec-octyl.

[0037]

[0039] In a fifteenth aspect, the present disclosure provides a method of any one of the eleventh to fourteenth aspects, wherein R 1 and R 1 is methyl.

[0038]

[0040] In a sixteenth aspect, the present disclosure provides the method of any one of the eleventh to fifteenth aspects, wherein the hydride reagent is NaBH4.

[0039]

[0041] In a seventeenth aspect, the present disclosure provides the method of any one of the eleventh to sixteenth aspects, wherein the dialkyl magnesium compound is MgMg(C2-C8 alkyl)2, Mg(C3-C8 alkyl)2, or Mg(C4-C8 alkyl)2.

[0040]

[0042] In an eighteenth aspect, the present disclosure provides the method of any one of the eleventh to seventeenth aspects, wherein the dialkyl magnesium compound is Mg(CH2CH2CH2CH3)2 or Mg[(CH)(CH3)(CH2CH3)][CH2CH2CH2CH3].

[0041]

[0043] In a nineteenth aspect, the present disclosure provides a compound of formula (II): TIFF0007733242000015.tif84170 [wherein M is selected from Hf, Zr, Ti, Ta, Nb, W, and Mo; In the formula, R 1 and R 1 is independently selected from hydrogen and C1-C8 alkyl, the method comprising: formula, TIFF0007733242000016.tif83170 with a compound of formula MX4, wherein X is chloro, bromo, or iodo.

[0042]

[0044] In a twentieth aspect, the present disclosure provides the method of the nineteenth aspect, wherein M is Hf, Zr, Ti, W, or Mo.

[0043]

[0045] In a twenty-first aspect, the present disclosure provides the method of the nineteenth or twentieth aspect, wherein R and R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, or sec-octyl.

[0044]

[0046] In a twenty-second aspect, the present disclosure provides the method of the nineteenth, twentieth, or twenty-first aspect, wherein R and R 1 is methyl.

[0045]

[0047] In a twenty-third aspect, the present disclosure provides a compound of formula (II): TIFF0007733242000017.tif84170, wherein M is Hf, Zr, Ti, Ta, Nb, W, or Mo, and X is chloro, bromo, or iodo, the compound having less than about 0.5 weight percent of multiply alkylated species as measured by gas chromatography.

[0046]

[0048] In a twenty-fourth aspect, the present disclosure provides a compound of the twenty-third aspect, wherein M is Hf, Zr, Ti, W, or Mo.

[0047]

[0049] In a twenty-fifth aspect, the present disclosure provides a compound of the twenty-third or twenty-fourth aspect, wherein the compound of formula (I) has less than about 0.3 weight percent or less than about 0.1 weight percent of multiply alkylated species.

[0048]

[0050] In a twenty-sixth aspect, the present disclosure provides a compound of the twenty-third, twenty-fourth, or twenty-fifth aspects, wherein the compound of formula (III) is further devoid of dicyclopentadiene species and mixed dicyclopentadiene species.

[0049]

[0051] While several exemplary embodiments of the present disclosure have been described above, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the claims appended hereto. Numerous advantages of the disclosure set forth in this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is, in many respects, merely illustrative. The scope of the disclosure, of course, is defined in the language in which the appended claims are expressed.

Claims

1. Formula (I): [Wherein R and R １ is hydrogen and C １ ~C ８ and wherein each of the groups is independently selected from alkyl, formula The compound ６ and contacting the Adding a hydride reagent A method comprising:

2. The hydride reagent is NaBH ４ , LiAlH ４ , LiBH ４ , LiBH(CH ３ CH ２ ) ３ , [(isobutyl) ２ AlBH ４ ], NaBH ３ CN, Na[HB(OC(O)CH ３ )], B.H. ３ -Tetrahydrofuran, BH ３ -S(CH ３ ) ２ , diisobutylaluminum hydride, or sodium bis(2-methoxyethoxy)aluminum hydride.

3. R and R １ 3. The method of claim 1 or 2, wherein is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, or sec-octyl.

4. R and R １ The method of claim 1 or 2, wherein is methyl.

5. The hydride reagent is NaBH ４ The method according to claim 1 or 2, wherein

6. The hydride reagent is NaBH ４ 3. The method of claim 1 or 2, wherein R and R1 are methyl.

7. 3. The method of claim 1 or 2, wherein the compound of formula (I) has less than 0.5 weight percent of compounds of formula (I) multiply alkylated on the cyclopentadiene ring.

8. The compound of formula (I) is of the formula 3. The method of claim 1 or 2, wherein the compound is devoid of compounds formed by dimerization of the compound of formula (I).

9. Formula (I): [Wherein R and R １ is hydrogen and C １ ~C ８ and wherein each of the groups is independently selected from alkyl, formula contacting a compound of formula providing a compound of formula (I) WCl ６ Adding Adding a hydride reagent A method comprising:

10. The hydride reagent is NaBH ４ , LiAlH ４ , LiBH ４ , LiBH(CH ３ CH ２ ) ３ , [(isobutyl) ２ AlBH ４ ], NaBH ３ CN, Na[HB(OC(O)CH ３ )], B.H. ３ -Tetrahydrofuran, BH ３ -S(CH ３ ) ２ 10. The method of claim 9, wherein the aluminum hydride is sodium bis(2-methoxyethoxy)aluminum hydride, diisobutylaluminum hydride, or sodium bis(2-methoxyethoxy)aluminum hydride.

11. The hydride reagent is NaBH ４ The method according to claim 9 or 10, wherein

12. R and R １ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, or sec-octyl.

13. R and R １ The method of claim 9 or 10, wherein is methyl.

14. The hydride reagent is NaBH ４ The method according to claim 9 or 10, wherein

15. The hydride reagent is NaBH ４ and R and R １ 11. The method of claim 9 or 10, wherein each of is methyl.

16. The dialkyl magnesium compound is di(C １ ~C ８ 11. The method of claim 9 or 10, wherein the compound is an alkyl magnesium compound.

17. The dialkyl magnesium compound is Mg(CH ２ CH ２ CH ２ CH ３ ) ２ or Mg[(CH)(CH ３ ) (CH ２ CH ３ ) ][CH ２ CH ２ CH ２ CH ３ 11. The method according to claim 9 or 10, wherein

Images