METHOD FOR PRODUCING AMIDINATE METAL COMPLEX

Abstract

To provide a method for producing an amidinate metal complex which is represented by [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM in cost saving and simple manner.

A method for producing an amidinate metal complex represented by [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM including: a first step in which R.sup.3X is reacted with a metal Li in a solvent to obtain R.sup.3Li solution with LiX suspended therein; a second step in which the R.sup.3Li solution with LiX existing therein is reacted with R.sup.1—N═C═N—R.sup.2 to obtain a [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution with the LiX suspended therein; a third step in which the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution with the LiX existing therein is reacted with MX to obtain an amidinate metal complex solution, represented by the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM, with the LiX suspended therein; and a fourth step for removing the LiX in the solution obtained by the third step.

Claims

1. A method for producing an amidinate metal complex {[R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM (where the R.sup.1 and the R.sup.2 are an alkyl group whose carbon number is 2 to 4 or an alkyl group having Si whose carbon number is 2 to 4; where the R.sup.3 is —C.sub.2H.sub.5 or —C.sub.3H.sub.7; where the n is 2 or 3; and where the M is Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, or Ru)}: wherein R.sup.3X is reacted with a metal Li in a solvent to obtain a R.sup.3Li solution with LiX suspended therein, R.sup.3Li in the solution with the LiX existing therein is reacted with R.sup.1—N═C═N—R.sup.2 to obtain a [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution with the LiX suspended therein, the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li in a solution with the LiX existing therein is reacted with MX to obtain a [R.sup.1—N—C(R..sup.3)—N—R.sup.2]nM solution with the LiX suspended therein, and thereafter the LiX (where the X is Cl, Br, or I; and where the X of the LiX may be the same as or different from the X of the MX) in the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM solution is removed.

2. The method for producing an amidinate metal complex according to claim 1, wherein the reaction of the R.sup.3Li with the R.sup.1—N═C═N—R.sup.2 is performed in a state where the LiX is substantially left in the R.sup.3Li solution.

3. The method for producing an amidinate metal complex according to claim 1, wherein the reaction of the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li with the MX is performed in a state where the LiX is substantially left in the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution.

4. The method for producing an amidinate metal complex according to claim 1, wherein the removal of the LiX in the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM solution is performed in such a manner that the solvent in the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM solution is replaced by a hydrocarbon-based solvent.

5. The method for producing an amidinate metal complex according to claim 1, wherein the removal of the LiX is performed by one or two or more operations selected from the group consisting of filtration, centrifugal separation, decantation, and distillation.

6. The method for producing an amidinate metal complex according to claim 1, wherein the reaction from the generation of the R.sup.3Li to the generation of [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM is performed in the same container.

7. The method for producing an amidinate metal complex according to claim 1, wherein the R.sup.1—N═C═N—R.sup.2 is N, N′-diisopropylcarbodiimide or N, N′-di-tert-butylcarbodiimide.

8. The method for producing an amidinate metal complex according to claim 1, wherein the MX is at least one chemical compound selected from the group consisting of YCl.sub.3, MnCl.sub.2, FeCl.sub.2, CoCl.sub.2, NiCl.sub.2, CuCl, AgCl, YBr.sub.3, MnBr.sub.2, FeBr.sub.2, CoBr.sub.2, NiBr.sub.2, CuBr, AgBr, YI.sub.3, MnI.sub.2, FeI.sub.2, CoI.sub.2, NiI.sub.2, Cut, and AgI.

9. The method for producing an amidinate metal complex according to claim 1, wherein the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM is a chemical compound used for depositing a M-based film.

Description

BRIEF DESCRIPTION OF DRAWINGS

Description of Embodiments

[0036] The present invention is directed to a method for producing [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM. The chemical compound {[R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM} is a chemical compound to be used for depositing a M-based film. The M-based film is a M metal film, a nitride M metal film, or an oxide M metal film. The M-based film is not limited thereto. For example, the M-based film is a carbonized M metal film. The chemical compound is an amidinatc metal complex used in the deposition, specially, performed by the ALD method. The method for producing [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM includes a first step for reacting R.sup.3X with a metal Li in a solvent to obtain a R.sup.3Li solution with LiX suspended therein. The method includes a second step for reacting the R.sup.3Li solution with the LiX existing (being left; being suspended) therein with R.sup.1-N═C═N—R.sup.2 to obtain a [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution with the LiX existing (being left: being suspended) therein. The method includes a third step for reacting the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li solution with the LiX existing (being left: being suspended) therein with MX to obtain an amidinate metal complex solution represented by the [R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM with the LiX existing (being left: being suspended) therein. The method includes a fourth step for removing the LiX in the solution obtained by the third step. The R.sup.1 and R.sup.2 represent an alkyl group whose carbon number is 2 to 4 or an alkyl group having Si whose carbon number is 2 to 4. The R.sup.3 is —C.sub.2H.sub.5 or —C.sub.3H.sub.7. Then is 2 or 3. The M is Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, or Ru. The X of the LiX and the X of the MX may be the same or may be different from each other.

[0037] The first step is represented by the following reaction formula (1).

R.sup.3X+2Li.fwdarw.R.sup.3Li+LiX  (1)

[0038] The second step is represented by the following reaction formula (2).

R.sup.3Li+LiX+R.sup.1—N═C═N—R.sup.2.fwdarw.[R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li+LiX  (2)

[0039] The third step is represented by the following reaction formula (3).

n{[R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li+LiX}+MXn.fwdarw.[R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM+nLiX+nLiX-tm (3)

[0040] In the above reaction formulas (2) and (3), the by-product LiX was normally removed. The reason is as follows. Namely, it has been conceived that the by-product LiX generated in the reaction of the preliminary performed steps (1) and (2) inhibits the subsequent reaction.

[0041] As per the reaction formulas (2) and (3) being represented by the following formulas of (2-1) and (3-1), the by-product LiX was normally removed.

[0042] Normally, the by-product LiX generated in the reaction [formula (1)] as the first step was removed prior to the second step (reaction).

[0043] Normally, the by-product LiX generated in the reaction [formula (2)] as the second step was removed prior to the third step (reaction).

[0044] This is troublesome.

[0045] To solve the above problem, in the present invention, the by-product LiX generated in the first step is not removed prior to the second step (reaction). Further, the by-product LiX generated in the second step is not removed prior to the third step (reaction). This provides good workability.

R.sup.3Li+R.sup.1—N═C═N—R.sup.2.fwdarw.[R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li  (2-1)

n[R.sup.1—N—C(R.sup.3)—N—R.sup.2]Li+MXn.fwdarw.[R.sup.1—N—C(R.sup.3)—N—R.sup.2]nM+nLiX  (3-1)

[0046] Preferably, the second step is performed in a state where the LiX is substantially left in the solution obtained by the first step. Further preferably, the second step is performed without performing the process for removing the LiX from the solution obtained by the first step (i.e., the second step is performed in a state where the LiX is left in the solution obtained by the first step). Specially preferably, the second step is performed without performing the process for removing the LiX from the solution obtained by the first step at all (i.e., the second step is performed in a state where the LiX is left in the solution obtained by the first step). This makes the process simple. Because the removal of the LiX is not performed, the complicated process can be eliminated. There was no hindrance when the second step (reaction) was performed even when the LiX was not removed.

[0047] Preferably, the third step is performed in a state where the LiX is substantially left in the solution obtained by the second step. Further preferably, the third step is performed without performing the process for removing the LiX from the solution obtained by the second step (i.e., the third step is performed in a state where the LiX is left in the solution obtained by the second step). Specially preferably, the third step is performed without performing the process for removing the LiX from the solution obtained by the second step (i.e., the third step is performed in a state where the LiX is left in the solution obtained by the second step). This makes the process simple. Because the removal of the LiX is not performed, the complicated process can be eliminated. There was no hindrance when the third step (reaction) was performed even when the LiX was not removed.

[0048] The solvent in the solution obtained by the third step is replaced by a hydrocarbon-based solvent to perform the removal of the LiX. The hydrocarbon-based solvent is, for example, n-hexane. The removal of the LiX is performed by one or two or more operations selected from the group consisting of filtration, centrifugal separation, decantation, and distillation.

[0049] The process from the first step to the third step is performed in the same container. More specifically, the entire process from the first step to the third step is performed in the same reaction container (reaction oven). This makes the process simple.

[0050] R.sup.1—N═C═N—R.sup.2 used in the second step is, for example, N, N′-diisopropyl carbodiimide, or N, N′-di-tert-butylcarbodiimide.

[0051] The MX used in the third step is, for example, YCl.sub.3, MnCl.sub.2, FeCl.sub.2, CoCl.sub.2, NiCl.sub.2, CuCl, AgCl, YBr.sub.3, MnBr.sub.2, FeBr.sub.2, CoBr.sub.2, NiBr.sub.2, CuBr, AgBr, YI.sub.3, MnI.sub.2, FeI.sub.2, CoI.sub.2, NiI.sub.2, CuI, or AgI.

[0052] Hereinafter, specific examples are described. The present invention, however, is not limited to those examples. It is to be understood that various modification examples and application examples will be embraced within the scope of the present invention unless otherwise the characteristics of the present invention degrade largely.

Example 1

[0053] [bis(N, N′-diisopropylpropion amidinate)cobalt]

[0054] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter; white solid) generated in the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropyl carbodiimide of 0.2 mol was slowly dropped into the suspension. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Cobalt chloride (CoCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylpropion amidinate)cobalt was about 90%.

[0055] In the above-described process, after the Li was completely consumed, the N, N′-diisopropylcarbodiimide was dropped. There was no problem even when the N, N′-diisopropylcarbodiimide was dropped in a state where a little Li was left.

Example 2

[0056] [bis(N, N′-diisopropylbutaneamidinate)cobalt]

[0057] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Cobalt chloride (CoCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)cobalt was about 89%.

Example 3

[0058] [bis(N, N′-diisopropylbutaneamidinate)cobalt]

[0059] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl bromide of 0.2 mol was dropped slowly. Lithium bromide (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Cobalt chloride (CoCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflex the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium bromide (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. The lithium bromide and the lithium chloride (both are insoluble matters) are obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)cobalt was about 53%.

Example 4

[0060] [bis(N-N′-di-tert-butylbutaneamidinate)cobalt]

[0061] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-di-tert-butylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Cobalt chloride (CoCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Sublimation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-di-tert-butylbutaneamidinate)cobalt was about 35%.

Example 5

[0062] [bis(N, N′-diisopropylpropionamidinate)iron]

[0063] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Iron chloride (FeCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was removed via decantation. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylpropionamidinate)iron was about 92%.

Example 6

[0064] [bis(N, N′-diisopropylbutaneamidinate)iron]

[0065] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Iron chloride (FeCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)iron was about 91%.

Example 7

[0066] [bis(N, N′-diisopropylpropionamidinate)manganese]

[0067] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Mangan chloride (MnCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylpropionamidinate)manganese was about 70%.

Example 8

[0068] [bis(N, N′-diisopropylbutaneamidinate)manganese]

[0069] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflex the diethyl ether. Agitation was performed at room temperature for four hours. Manganese chloride (MnCl.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)manganese was about 76%.

Example 9

[0070] [bis(N, N′-diisopropylpropionamidinate)magnesium]

[0071] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Magnesium bromide (MgBr.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. By distillation under reduced pressure (0.1 torr) , bis(N, N′-diisopropylpropionamidinate)magnesium was separated from the lithium chloride and the lithium bromide. A yield of thus obtained bis(N, N′-diisopropylpropionamidinate)magnesium was about 63%.

Example 10

[0072] [bis(N, N′-diisopropylbutaneamidinate)magnesium]

[0073] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Magnesium bromide (MgBr.sub.2) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride and the lithium bromide (both are by-products) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. The lithium chloride and the lithium bromide (both are insoluble matters) were obtained via filtration. The solvent was distilled away. Distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)magnesium was about 79%.

Example 11

[0074] [bis(N, N′-di-isopropylbutaneamidinate)nickel]

[0075] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, n-propyl chloride of 0.2 mol was dropped slowly. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. A nickel chloride dimethoxyethane adduct (NiCl.sub.2.Math.DME) of 0.1 mol was added into the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Then, distillation under reduced pressure (0.1 torr) was performed. A yield of thus obtained bis(N, N′-diisopropylbutaneamidinate)nickel was about 80%.

Example 12

[0076] [(N, N′-diisopropylpropionamidinatecopper).sub.2]

[0077] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Copper chloride (CuCl) of 0.2 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. Lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Sublimation under reduced pressure (0.1 torr) was performed. A yield of the (N, N′-diisopropylpropionamidinatecopper).sub.2 as thus obtained dimer was about 50%.

Example 13

[0078] [(N, N′-diisopropylpropionamidinatesilver).sub.2]

[0079] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.4 mol lithium and 250 ml diethyl ether, ethyl chloride of 0.2 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.2 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Silver bromide (AgBr) of 0.2 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride and the lithium bromide (both are insoluble matters) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. The lithium chloride (insoluble matter) of 0.4 mol was obtained via filtration. The solvent was distilled away. Sublimation under reduced pressure (0.1 torr) was performed. A yield of the (N, N′-diisopropylpropionamidinatesilver).sub.2 as thus obtained dimer was about 53%.

Example 14

[0080] [tris(N, N′-diisopropylpropionamidinate)yttrium]

[0081] Reaction was performed under an inert gas atmosphere. Into a flask containing 0.6 mol lithium and 300 ml diethyl ether, ethyl chloride of 0.3 mol was dropped slowly. The ethyl chloride was in a state of liquid by being cooled. The lithium chloride (by-product: insoluble matter: white solid) generated with the progress of the reaction was suspended. After the dropping, the lithium was completely consumed. N, N′-diisopropylcarbodiimide of 0.3 mol was slowly dropped into the suspension solution. Reaction heat occurred to reflux the diethyl ether. Agitation was performed at room temperature for four hours. Yttrium chloride (YCl.sub.3) of 0.1 mol was added to the suspended reaction mixture. Reaction heat occurred to reflux the diethyl ether. Agitation was performed for 24 hours. In the above-described process, removal of the lithium chloride (by-product) was not performed at all. All the reactions in the above-described process were performed in the same flask. A solvent was distilled away. N-hexane of 500 ml was added thereto. The lithium chloride (insoluble matter) of 0.6 mol was obtained via filtration. The solvent was distilled away. Sublimation under reduced pressure (0.1 torr) was performed. A yield of thus obtained tris(N, N′-diisopropylpropionamidinate)yttrium was about 55%.