Mono-substituted cyclopentadienes and metal cyclopentadienyl complexes and synthesis methods thereof

Patent metadata

Field	Value
Publication number	US-11274069-B2
Application number	US-202016992721-A
Country	US
Kind code	B2
Filing date	Aug 13, 2020
Priority date	Aug 13, 2020
Publication date	Mar 15, 2022
Grant date	Mar 15, 2022

Abstract

Disclosed are mono-substituted cyclopentadienes, metal cyclopentadienyl complexes and methods for synthesizing them. The disclosed mono-substituted cyclopentadienes are synthesized by a selective catalytic carbon-carbon coupling reaction. The disclosed metal cyclopentadienyl complexes are synthesized from the disclosed mono-substituted cyclopentadienes. The disclosed metal cyclopentadienyl complexes include main group metal and transition metal cyclopentadienyl complexes, and may be used as deposition precursors contained in film forming compositions for film depositions in semiconductor industry, such as ALD, CVD, SOD, etc.

First claim

What is claimed is:

1. A method of synthesizing a mono-substituted cyclopentadiene, the method comprising:
mixing a metal hydroxide, a halide, a cyclopentadiene monomer, an alkaline earth oxide, and a homogeneous catalyst in a solvent; and
allowing a selective catalytic carbon-carbon coupling reaction to form the mono-substituted cyclopentadiene,
wherein approximately 20-400% excess amount of the cyclopentadiene monomer is used relative to the amount of the halide.

2. The method of claim 1 , further comprising:
contacting the mono-substituted cyclopentadiene with a metal compound; and
converting the mono-substituted cyclopentadiene to a metal cyclopentadienyl complex.

3. The method of claim 2 , further comprising:
maintaining a temperature within a range of from −15° C. to 70° C. under atmospheric pressure.

4. The method of claim 2 , further comprising:
optionally purifying the mono-substituted cyclopentadiene.

5. The method of claim 1 , wherein approximately 40-80% excess amount of the cyclopentadiene monomer is used relative to the amount of the halide.

6. The method of claim 1 , wherein the metal hydroxide is MOH, wherein M is Group I alkali metal.

7. The method of claim 1 , wherein the halide is an silyl-, amino-, alkyl- or hydrocarbonyl halide or fluoroalkyl halide has the formula R(Hal) or R(F)(Hal), wherein Hal is selected from Cl, Br, I; R is selected from
a. a C 1 -C 8 linear or branched, saturated or unsaturated hydrocarbyl group;
b. a C 1 -C 8 linear or branched, saturated or unsaturated fluorohydrocarbyl group containing at least one fluorine;
c. a silyl group [SiR′ 3 ] with R′ being selected from H, a C 1 -C 4 saturated or unsaturated hydrocarbyl group;
d. a silyl group [SiR′ 3 ] with each R′ being selected from H, F, a C 1 -C 4 saturated or unsaturated fluorohydrocarbyl group containing at least one fluorine atom; and
e. an amino group [—NR 1 R 2 ] with each R 1 and R 2 being independently selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group.

8. The method of claim 1 , wherein the alkaline earth oxide is MO, wherein M is Group II alkaline earth metal.

9. The method of claim 1 , wherein the catalyst is a tertiary phosphonium salt.

10. The method of claim 9 , wherein the catalyst is tetrabutylphosphonium chloride, Bu 4 PCl (CAS No: 2304-30-5).

11. The method of claim 2 , wherein the metal compound is a Group I, Group II and Group III main group metal compound or a transition metal compound.

12. The method of claim 2 , wherein the metal compound is an alkyl metal compound alkyl-M, where M is Group I, Group II and Group III main group metal or a transition metal.

13. The method of claim 12 , wherein the alkyl metal compound is selected from MeLi or BuLi.

14. The method of claim 2 , wherein the metal compound is a metal hydride MH, wherein M is a Group I, Group II or Group III main group metal or a transition metal.

15. The method of claim 14 , wherein the metal hydride MH, wherein M is selected from K, Na, Sr, Ba, Ga, In, Y or Yb.

16. The method of claim 1 , wherein the solvent is THF or Me-THF.

17. The method of claim 1 , wherein the mono-substituted cyclopentadiene is 1-fluorobutyl-cyclopentadiene (C 5 H 5 -1-F—C 4 H 10 , C 5 H 5 -1-F-Bu), 2-pentyl-cyclopentadiene (C 5 H 5 -2-C 5 H 11 , C 5 H 5 -2-Pent), 2-butyl-cyclopentadiene (C 5 H 5 -2-C 4 H 9 , C 5 H 5 -2-Bu), or 1,1,1-trifluoropropyl-cyclopentadiene (C 5 H 5 -1,1,1-3F—C 4 H 6 , C 5 H 5 -3F-Bu).

18. The method of claim 1 , wherein the mono-substituted cyclopentadiene is 1-fluorobutyl-cyclopentadiene (C 5 H 5 -1-F—C 4 H 10 , C 5 H 5 -1-F-Bu).

19. The method of claim 2 , wherein the metal cyclopentadienyl precursor is Li(C 5 H 4 -2-C 5 H 11 ) (Li(Cp-2-Pent), CAS No: 2413046-23-6), K(C 5 H 4 -2-C 5 H 11 ) (K(Cp-2-Pent)), Na(C 5 H 4 -2-C 5 H 11 ) (Na(Cp-2-Pent)), K(C 5 H 4 -1-F—C 4 H 10 ) (K(Cp-1-F-Bu)), K(C 5 H 4 -1,1,1-3F—C 4 H 6 ) (K(Cp-1,1,1-3F-Bu)), Li(C 5 H 4 -2-C 4 H 9 ) (Li(Cp-2-Bu)), or In(C 5 H 4 -2-C 5 H 11 ) (In(Cp-2-Pent), CAS No.: 2364634-67-1).

20. The method of claim 2 , wherein the metal cyclopentadienyl precursor is Li(C 5 H 4 -2-C 5 H 11 ) (Li(Cp-2-Pent), CAS No: 2413046-23-6).

21. The method of claim 2 , wherein the metal cyclopentadienyl precursor is K(C 5 H 4 -2-C 5 H 11 ) (K(Cp-2-Pent)).

22. The method of claim 2 , wherein the metal cyclopentadienyl precursor is K(C 5 H 4 -1-F—C 4 H 10 ) (K(Cp-1-F-Bu)).

23. The method of claim 2 , wherein the metal cyclopentadienyl precursor is Na(C 5 H 4 -2-C 5 H 11 ) (Na(Cp-2-Pent)).

24. The method of claim 2 , wherein the metal cyclopentadienyl precursor is In(C 5 H 4 -2-C 5 H 11 ) (In(Cp-2-Pent), CAS No.: 2364634-67-1).

Assignees

• Air Liquide

Inventors

• Nikiforov Grigory

Classifications

• B01J2531/90

  Catalytic systems characterized by the solvent or solvent system used · CPC title

• B01J31/0268

  Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title

• C07C17/38

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C2/86 Primary

  by condensation between a hydrocarbon and a non-hydrocarbon · CPC title