KR101150124B1 - Method for preparing metal complexes of polydentate beta-ketoiminates - Google Patents

Abstract

상기 식에서, M은 Mg, Ca, Sr 및 Ba로 이루어진 군으로부터 선택된 금속이며; R¹, R³, R⁵ 및 R⁶은 독립적으로 알킬기, 플루오로알킬기, 지환족기, 및 아릴기로부터 선택되며; R²는 수소 원자, 알킬기, 알콕시기, 지환족기, 및 아릴기로부터 선택되며; R⁴는 알케닐 브릿지이며; R⁷ 및 R⁸은 독립적으로 알킬기 및 아릴기로부터 선택된다.The present invention provides a compound represented by the following formula A comprising reacting M in a reaction mixture comprising a tridentate ketoimine ligand and an alcohol comprising at least one selected from the group consisting of R ⁷ OH and (OH) _n R ⁸ The present invention relates to a method for producing a group metal-containing multidentate β-ketoiminate. In certain embodiments, the reaction mixture further comprises an organic solvent.

Wherein M is a metal selected from the group consisting of Mg, Ca, Sr and Ba; R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge; R ⁷ and R ⁸ are independently selected from alkyl groups and aryl groups.

Description

METHOD FOR PREPARING METAL COMPLEXS OF MULTI BETA KETOIMINATE {METHOD FOR PREPARING METAL COMPLEXES OF POLYDENTATE BETA-KETOIMINATES}

Cross Reference to Related Application

This application claims priority to US Provisional Application No. 61 / 159,237, filed March 11, 2009.

In the semiconductor manufacturing industry, metal-containing precursors are used in chemical vapor deposition methods including atomic layer deposition to produce uniform metal containing films on substrates such as silicon, metal nitrides, metal oxides and other metal containing layers. There is a continuing need for precursors containing metal sources. To this end, methods for producing metal source containing precursors at higher yields and, in certain instances, at lower cost than conventional methods, would be desired in the semiconductor manufacturing industry. In addition, methods of making such precursors for preparing metal source containing precursors while minimizing possible metal impurities, such as, but not limited to, lithium, sodium, potassium, and combinations thereof, that may be incorporated during the manufacturing process. It is requested.

Conventional methods for the preparation of polydentate β-ketoiminate ligands include bulk ketones in the presence of strong bases such as sodium amide or sodium hydride, as shown in the multistage scheme of Scheme 1 below. Following well-known procedures such as Claisen condensation of ethyl esters, other well known procedures such as Schiff base condensation reactions with alkylaminoalkylamines are carried out:

Scheme 1

Another method for preparing metal-containing complexes is to react tridentate β-ketoiminate ligands with Group 2 metals in the presence of ammonia, metal amides, metal hydrides, or metal alkoxides, as shown in Scheme 2 below. Includes sikim.

Scheme 2

The metal-containing complex may also be reacted with an alkyl lithium or potassium hydride with an alkyl lithium or potassium hydride to yield a lithium or potassium salt of the ligand, as shown in Scheme 3 below, wherein the formula MX ₂ (X = It can be prepared by reacting with a metal halide having Cl, Br, I):

Scheme 3

However, reactions such as Scheme 2 using Group 2 metals in the presence of ammonia may not be suitable for larger scale processes because bubbling ammonia is a tedious process and the reaction yields are typically very low. In addition, reactions such as Scheme 1 and Scheme 3, including sodium hydride or potassium hydride as reagents, are not desired because of their high reactivity which may cause potential fires in addition to sodium or potassium impurities in the final product. Another reaction using metal amides or metal alkoxides as reagents, such as Scheme 2, is not practical because such reagents are too expensive.

Described herein are methods for making Group 2 metal containing multidentate β-ketoiminates, wherein the multidentate β-ketoiminate contains nitrogen or oxygen functional groups in the imino group. In one embodiment, the Group 2 metal multidentate β-ketoiminate is selected from the group represented by Formula A:

In Formula A, M is a metal selected from the group consisting of Mg, Ca, Sr and Ba; R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge. In one embodiment, R ⁴ is an alkenyl bridge, such as, but not limited to, a group containing two or three carbon atoms, thereby forming a five or six member coordination ring in the metal center. In this or other embodiments, any one or more of the substituents R ¹ , R ² , R ³ , R ⁵ and R ⁶ may be linked to form a ring. In this or other embodiments, the ring may further comprise a carbon atom, an oxygen atom, and / or a nitrogen atom.

In one aspect, represented by Formula A comprising reacting M in a reaction mixture comprising a tridentate ketoimine ligand and an alcohol comprising at least one selected from the group consisting of R ⁷ OH and (OH) _n R ⁸ Methods of preparing Group 2 metal containing multidentate β-ketoiminates are provided:

Wherein M is a metal selected from the group consisting of Mg, Ca, Sr and Ba; R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge;

R ⁷ and R ⁸ are independently selected from alkyl groups and aryl groups.

In certain embodiments, the reaction mixture further comprises an organic solvent.

Several advantages can be achieved by the methods described for producing metal containing multidentate β-ketoiminates, including the following:

The ability to form reactive metal-containing multidentate β-ketoiminates in higher yields compared to previously available manufacturing methods;

The ability to remove possible metal impurities such as, but not limited to, lithium, sodium or potassium in the metal containing multidentate β-ketoiminate;

The ability to remove possible halide impurities from metal containing multidentate β-ketoiminates using pure metals instead of metal halides in conventional methods; And / or

Ability to simplify the process and reduce manufacturing costs.

The method described herein is a method for preparing Group 2 metal containing multidentate β-ketoiminates that can avoid yield reduction, slow reaction time, and / or problems of impurity incorporation into the final product. The method described herein avoids these problems by incorporating a metal, such as a pure Group 2 metal, an alcohol, and a tridentate ketoimine ligand into the reaction mixture. It is believed that the presence of alcohol in the reaction mixture further reacts with the tridentate ketoiminate ligand to form metal alkoxides in situ which form multidentate β-ketoiminate final products. Conventional production methods teach that it is not possible to produce metal containing multidentate β-ketoiminates, in particular strontium complexes, using pure Sr metal as starting material. Thus, using a reaction mixture comprising an Sr metal, one or more alcohols such as isopropyl alcohol (IPA) and a tridentate ketoimine ligand, to provide a higher relatively high yield, for example greater than 80%. The production of metal containing multidentate β-ketoiminate complexes, such as strontium complexes, is surprising and unexpected. In certain embodiments, Group 2 metals, such as Sr metals, are pure metals. As used herein, the term "pure" means that it comprises at least 99% Group 2 metal as measured by an inductively coupled plasma mass spectrometer (ICP-MS).

The methods described herein provide one or more of the following advantages over other methods currently available. First, the method can use relatively inexpensive reagents. For example, in certain embodiments, the method may use Group 2 metals rather than commonly used reagents such as Group 2 metal amides. Nowadays, Group 2 metals in their pure form are more cost effective than metal amides, which are usually produced by reactions between metal halides and sodium amide or potassium amide. Second, the methods described herein can prevent the use of sodium hydride or potassium hydride to form group 2 metal amides. Instead, in the process described herein, the reaction by-product of the pure Group 2 metal and the tridentate ketoimine is hydrogen which is more easily removed from the final product mixture and / or not harmful impurities in the final product mixture. The alcohol is believed to provide reflux in the reaction mixture during the reaction to form reactive Group 2 metal alkoxide in situ and further react with tridentate ketoimine to form the final product. In certain embodiments, alcohols and unreacted tridentate ketoimine ligands, and solvents, can be readily removed from the reaction mixture using distillation, fractionation, stripping, or other means.

Group 2 metal-containing multidentate β-ketoiminates are selected from the group represented by formula (A):

In Formula A, M is a metal selected from the group consisting of Mg, Ca, Sr and Ba; R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge. In Formula A, and throughout the specification, the term "alkyl" means a linear, branched, or cyclic functional group having 1 to 20, or 1 to 12, or 1 to 6 carbon atoms. . Representative alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, isopentyl, and tertiary Pentyl, including but not limited to. The term "alkyl" also applies to alkyl moieties included in other groups such as haloalkyl, fluoroalkyl, alkaryl, or aralkyl. In Formula A and throughout the specification, the term “fluoroalkyl” refers to a linear, branched form having from 1 to 20, or from 1 to 12, or from 1 to 6 carbon atoms and at least one fluorine atom. Or cyclic functional group. In Formula A and throughout the specification, the term “alicyclic group” includes at least one cyclic group having a saturated or unsaturated cyclic group having 3 to 20, or 3 to 12, or 3 to 6 carbon atoms. It means an aliphatic group. In Formula A and throughout the specification, the term “aryl” means a cyclic functional group having 6 to 12 carbon atoms. Representative aryl groups include, but are not limited to, phenyl, benzyl, tolyl, and o-xylyl. In Formula A and throughout the specification, the term “alkenyl” connects two nitrogen atoms to form a bridge and has 2 to 20, or 2 to 12, or 2 to 6 carbon atoms A group capable of connecting atoms or atoms in a ring of atoms. Representative alkenyl groups include, but are not limited to,-(CH ₂ ) ₂ -,-(CH ₂ ) _3- , -CH (Me) CH _2- , -CH ₂ CH (Me)-, wherein "Me" Is methyl. In Formula A and throughout the specification, the term “alkoxy” is linked to an oxygen atom (eg, RO) and has from 1 to 20, or from 1 to 12, or from 1 to 6 carbon atoms It means an alkyl group which can be. Representative alkoxy groups include, but are not limited to, methoxy (-OCH ₃ ) and ethoxy group (-OCH ₂ CH ₃ ). In certain embodiments, one or more of the alkyl, aryl and / or alkoxy groups may be substituted or unsubstituted, or may be substituted with one or more atoms or groups of atoms instead of hydrogen atoms. Representative substituents include, but are not limited to, oxygen, sulfur, halogen atoms (eg, F, Cl, I or Br), nitrogen, and phosphorus.

In one embodiment, R ⁴ is an alkenyl bridge, such as but not limited to a group containing two or three carbon atoms, thereby forming a five or six member coordination ring in the metal center. The substituent R ⁴ may be a linear alkenyl bridge or a branched alkenyl bridge. In one embodiment, R ⁴ is a linear alkenyl bridge, eg,-(CH ₂ CH ₂ )-and-(CH ₂ CH ₂ CH ₂ )-, but is not limited to this example. In other embodiments, R ⁴ is a branched alkenyl bridge, such as —CH (Me) CH ₂ — and —CH ₂ CH (Me) —, but is not limited to this example. As used herein, the term "Me" refers to a methyl group. In this or other embodiments, any one or more of the substituents R ¹ , R ² , R ³ , R ⁵ and R ⁶ may be linked to form a ring. In this or other embodiments, the ring may further comprise carbon, oxygen and / or nitrogen atoms.

Group 2 metal-containing multidentate β-ketoiminates are prepared in a reaction mixture comprising tridentate ketoimines represented by Formula B:

In Formula B, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently the same as described for Formula A above.

In the methods described herein, at least a portion of the reaction between the Group 2 metal and the tridentate ketoimine ligand occurs in the presence of at least one alcohol reagent. In this regard, the total alcohol input, or a portion thereof, may be added before the start of the reaction, continuously during the reaction step, or in combination thereof. Suitable alcohols include alcohols having the formula (I): R ⁷ OH. In formula (I), R ⁷ is linear, minute, such as, but not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof Aryl or alkyl moieties containing 1 to 20, or 1 to 12, or 1 to 6 carbon atoms that are topographic, or cyclic. In certain embodiments, the alcohol is n-butanol, isopropanol, ethanol, n-propanol, methanol, propanol, isobutanol, pentanol, isoamyl alcohol, 2-ethyl-1-hexanol, 2-methyl-1-butanol and Combinations thereof. Still other alcohol reagents include oligomeric or polymeric alcohols or polyols such as, but not limited to, poly (tetrahydrofuran), poly (propylene glycol), 1,4-butanediol, and combinations thereof. Another representative alcohol reagent includes compounds having the formula (II): (OH) _n R ⁸ , wherein R ⁸ is any aryl, any linear alkyl, branched alkyl, which may be substituted or unsubstituted , Cyclic alkyl, or a combination of alkyl and / or alkenyl groups, where n is the number of hydroxyl groups attached. As used herein, the term “substituted” means that the alkyl group and / or alkenyl group may contain atoms of one or more other elements, such as atoms other than oxygen, nitrogen, sulfur and / or carbon atoms. In certain embodiments, one or more of the alkyl groups and / or alkenyl groups may be substituted with oxygen atoms. Examples of suitable R ⁸ groups are-(CH ₂ ) ₁₁ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -,-[CH ₂ -CH ₂ -CH ₂ -CH ₂ -0] _m -CH ₂ -CH ₂ -CH ₂ -CH _2- , and-[CH ₂ -CH ₂ -0] _m -CH ₂ -CH _2- , but is not limited thereto, where m refers to the number of repeat units. Among the above, it is preferable that the alcohol reagent in the reaction mixture can be easily removed from the final product mixture without damaging the final product. In another embodiment, the alcohol may be present in the final product mixture in an amount of up to 5% by weight of the final product mixture, or up to 0.5% by weight of the final product mixture. The amount of alcohol present in the reaction mixture may be from 0.1 to 5.0 moles per mole of Group 2 metal M, preferably the ratio of alcohol to metal M may be 2.0.

In certain embodiments, the reaction mixture further comprises one or more solvents. Examples of suitable solvents include, but are not limited to, organic solvents such as hexane, benzene, toluene, tetrahydrofuran (THF), ethers and acetone. In certain embodiments, it is preferred that the solvent or mixture thereof is selected such that at least one of the reagents, reaction products, or combinations thereof in the reaction mixture is at least partially soluble. In other embodiments, the alcohol in the reaction mixture acts as both a reagent and a solvent.

In one particular embodiment of the methods described herein, the Group 2 metal containing multidentate β-ketoiminate is a reaction mixture comprising pure Group 2 metals, tridentate ketoimine ligands and alcohol reagents in an organic solvent or mixture of organic solvents. Is manufactured in. In certain embodiments, the metal and the tridentate ketoimine ligand are added in an organic solvent followed by the addition of alcohol. In this or other embodiments, alcohol is added “portion wise” to the reaction mixture to prevent sudden exothermic reactions. As used herein, the term “partly” refers to adding funnels to a reaction vessel in which a portion of the total amount of alcohol that is pure or diluted with an organic solvent contains the reaction mixture (eg, metal, tridentate ketoimine ligand, and organic solvent). It is added until the entire amount of alcohol is added. In this regard, the amount of alcohol is added in portions in order to prevent a sudden exothermic reaction. In certain embodiments, each portion can be, for example, 10 milliliters (ml) to 100 ml. However, the partial amount of alcohol filled in the reaction mixture may vary depending on the production scale. In this or other embodiments, the reaction mixture is refluxed at the boiling point of the organic solvent. In one specific embodiment, the reaction mixture comprises refluxing a pure metal, a tridentate ketoimine ligand, one or more alcohols such as IPA, and a solvent such as tetrahydrofuran (THF) as shown in Scheme 4 below. After filtration and removal of all volatiles was found to give the target complex in good yield:

The reaction mixture is exposed to conditions sufficient to provide a final product mixture containing Group 2 metal containing multidentate β-ketoiminates. There are several ways in which the methods described herein can be performed. In certain preferred embodiments, the reaction mixture is heated for a sufficient time for this at a temperature sufficient to react the reagents contained therein and form the final product mixture. Depending on the reagents contained in the reaction mixture, the reaction temperature may range from room temperature to 200 ° C., or the reflux temperature of the solvent used or the boiling point thereof. The reaction time can be about 0 hours or moments to about 100 hours, or about 0 to about 60 hours, or about 4 to about 48 hours. In certain embodiments, volatiles after the reaction can be removed from the final product mixture by standard procedures such as distillation, chromatography, recrystallization and / or titration. In this or other embodiments, the amount of unreacted material present in the final product mixture may be sufficiently low due to the volatility of the material (eg up to 5% by weight of the final product mixture) or the material is acceptable in the product. Possible impurities may remain in the final product mixture.

In one embodiment, the reaction mixture may be reacted at a suitable temperature and pressure under full reflux conditions for a time sufficient to achieve the main reaction of the Group 2 metal with alcohol, tridentate ketoimine ligand, or both. This conversion is sufficient if the concentration of ketoimine in the reactor is reduced to the point at which its volatility no longer matters in terms of operability or yield.

The teachings of the methods described herein include a large capacity (production rate above 1000 standard liters), a medium bench capacity (production rate of 10 to 1000 standard liters), small capacity (production rate below 10 standard liters), and all of the capacity between them. Applicable for

Examples of metal containing multidentate β-ketoiminates that can be prepared using the methods described herein are bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N , 0, N ') strontium, bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N') strontium, bis (2, 2-dimethyl-5- (1-ethylmethylaminoethyl-imino) -3-hexanonato-N, 0, N ') strontium, bis (2,2-dimethyl-5- (1-methylethylamino- 2-propylimino) -3-hexanoneto-N, O, N ') strontium, bis (2,2-dimethyl-5- (1-diethylaminoethyl-imino) -3-hexanoneito- N, 0, N ') strontium, and bis (2,2-dimethyl-5- (1-diethylamino-2-propylimino) -3-hexanoneto-N, O, N') strontium However, it is not limited thereto.

The methods described herein may be described using specific alphabetic characters, such as in the summary and claims of the invention. This does not mean including a time series order. In addition, unless otherwise specified, the method or process steps may be performed in a variety of different orders, eg, simultaneously, sequentially, and the like.

Although the method described herein is described in more detail with reference to the following examples, it will be understood that the method is not limited to the following examples.

Comparative Example 1

Synthesis of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium using strontium amide

_{40.0 g Sr (N (SiMe 3} ) 2) of (0.066 mol) _2? 2THF was charged to a 500 mL THF with a 100 ml flask shrink (Schlenk flask). To this flask was added dropwise 29.0 g (0.14 mol) waxy 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanone in 100 mL of THF. The pale yellow clear solution obtained was stirred overnight at room temperature. All volatiles were then removed in vacuo to yield a yellow solid which was dissolved in 100 mL of hot hexane. GC / MS analysis of the trapped volatile liquid showed that the liquid contained THF and hexamethylsilylamine as a byproduct. In the yellow solid GC / MS dissolved in THF, only 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanone was present in addition to THF, indicating that the solid was tridentate β -Implies ketoiminate ligands. The hexane solution was then concentrated to about 30 mL to precipitate white crystals at the bottom. The flask was kept at -20 ° C to obtain additional colorless crystals. 26.1 g of crystals were collected and dried under vacuum. The yield is 77% based on strontium.

Elemental Analysis: Theory for C ₂₄ H ₄₆ N ₄ O ₂ Sr: C, 56.49; N, 10.98; H, 9.09. Found: C, 56.34; N, 11.32; H, 8.91.

Example 1

Synthesis of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium with pure Sr metal and isopropanol

To 44.30 g (505.63 mmol) strontium metal, 214.69 g (1011.26 mmol) 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanone in 175 mL THF was added directly. 60.78 g (1011.26 mmol) isopropanol was added slowly using an addition funnel. The reaction flask was equipped with a condenser and evacuated under an argon source. The reaction mixture was refluxed for 16 hours, after which it became a solution with a small amount of particles at the bottom of the flask. The reaction was cooled to room temperature and filtered through a thin layer of celite (512 medium) on top of medium porosity frit. The orange-yellow filtrate was pumped under vacuum overnight to yield 250 g yellow solid in 97% crude yield. Recrystallization with hexane gave the pure product, which was identified by proton NMR and TGA to be the same compound as described in Comparative Example 1.

Comparative Example 2

Synthesis of Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium using strontium amide

To a solution of 1 g (1.81 mmol) Sr (N (SiMe ₃ ) ₂ ) ₂ ? (THF) ₂ in 10 mL THF 0.82 g (3.62 mmol) 2,2-dimethyl-5- (1- in 10 mL THF Dimethylamino-2-propylimino) -3-hexanone was added dropwise at room temperature. The reaction mixture was stirred for 16 hours. THF was evaporated under vacuum to give an off-white solid which was obtained as a solution in hexane. Hexane was removed to give a solid, which was recrystallized in pentane at room temperature. 0.48 g of clear needle shaped crystals were obtained (50% yield based on Sr).

Elemental Analysis: Theory for C ₂₆ H ₅₀ N ₄ O ₂ Sr: C, 58.01; N, 10.40; H, 9.36. Found: C, 56.07; N, 10.10; H, 8.86.

Example 2

Synthesis of Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanoneito-N, O, N ') strontium with pure Sr metal and isopropanol

After direct addition of 179.48 g (792.88 mmol) 2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanone to 43.42 g (495.55 mmol) strontium metal in 250 mL THF 60.70 mL (792.88 mmol) isopropanol was added. The reaction mixture was refluxed for 16 hours and upon completion an amber-red solution formed which was cooled to room temperature. The reaction mixture was filtered through a thin layer of medium grade celite on top of medium porosity frit. THF was pumped from the filtrate under vacuum to give a viscous dark red oil. The oil was dissolved in hexane and pumped again using a means to pump residual THF under vacuum. There was 240.04 g tar oil in 90% yield. It was recrystallized from octane to give the pure product, which was identified by proton NMR and TGA to be the same compound as described in Comparative Example 2.

Example 3

Synthesis of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium with pure Sr metal and tert-butanol

10.44 g (46.11 mmol) 2,2-dimethyl in 50 mL THF using cannula after direct addition of 8.68 g (46.11 mmol) tert-butanol to a piece of 2.02 g (23.05 mmol) of strontium metal in 75 mL THF -5- (1-dimethylamino-2-propylimino) -3-hexanone was added. The reaction was refluxed for 3 days to yield a grey-green suspension. The reaction was cooled down and filtered. The filtrate was evaporated under reduced pressure to give 11.0 g beige waxy solid with 94% crude yield. It was recrystallized in hexane to give the pure product, which was identified by proton NMR and TGA to be the same compound as described in Comparative Example 2.

Claims (19)

Group 2 metal-containing multidentate β-ketoiminate represented by the following Formula A comprising reacting M in a reaction mixture comprising a tridentate ketoimine ligand, and an alcohol comprising at least one selected from the group consisting of R ⁷ OH How to manufacture:

Wherein M is a metal selected from the group consisting of Mg, Ca, Sr and Ba; R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge;
R ⁷ is independently an alkyl group which is a linear, branched or cyclic functional group having 1 to 6 carbon atoms. The method of claim 1 wherein M comprises strontium. The method of claim 1, wherein the tridentate ketoimine ligand comprises a compound represented by Formula B:

Wherein R ¹ , R ³ , R ⁵ and R ⁶ are independently selected from alkyl groups, fluoroalkyl groups, alicyclic groups, and aryl groups; R ² is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alicyclic group, and an aryl group; R ⁴ is an alkenyl bridge. delete The process of claim 1, wherein the alcohol is methanol, ethanol, n-propanol, iso-propanol, n-butanol, secondary-butanol, iso-butanol, n-pentanol, neo-pentanol, tert-pentanol, and And a combination thereof. The process of claim 1 wherein the molar ratio of M to alcohol in the reaction mixture is from 0.1 to 5. The method of claim 1 wherein the reaction mixture further comprises an organic solvent. 8. The method of claim 7, wherein the organic solvent comprises toluene and hexane. 8. The method of claim 7, wherein the organic solvent comprises tetrahydrofuran. 8. The process of claim 7, wherein the reaction step is carried out in the presence of an organic solvent in which at least one of the tridentate ketoimine ligand and the alcohol is part or all soluble. 8. The method of claim 7, wherein the alcohol is added after the metal and the tridentate ketoimine ligand are added to the organic solvent. The method of claim 11, wherein alcohol is added portionwise to the reaction mixture to prevent sudden exothermic reactions. 8. The process of claim 7, wherein the reaction mixture is refluxed at the boiling point of the organic solvent. 2. The metal-containing multidentate β-ketoiminate of claim 1, wherein bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium How to include. The metal-containing multidentate β-ketoiminate according to claim 1, wherein the bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanoneito-N, O, N Method of containing strontium. The metal-containing multidentate β-ketoiminate of claim 1, wherein the bis (2,2-dimethyl-5- (1-ethylmethylaminoethyl-imino) -3-hexanoneito-N, O, N ' A method comprising strontium. The method of claim 1, wherein the metal-containing multidentate β-ketoiminate is selected from bis (2,2-dimethyl-5- (1-methylethylamino-2-propylimino) -3-hexanoneito-N, O, N ') a method comprising strontium. The method of claim 1, wherein the metal-containing multidentate β-ketoiminate is bis (2,2-dimethyl-5- (1-diethylaminoethyl-imino) -3-hexanoneito-N, O, N ' A method comprising strontium. The method of claim 1, wherein the metal-containing multidentate β-ketoiminate is selected from bis (2,2-dimethyl-5- (1-diethylamino-2-propylimino) -3-hexanoneito-N, O, N ') a method comprising strontium.