KR100892573B1 - Novel manganese amino-alkoxide complexes and process for preparing thereof - Google Patents

Abstract

A method for preparing a manganese amino-alkoxide compound used as a manganese precursor is provided to easily produce manganese oxide and manganese even at a low temperature by coordinating dialkylamino radical to manganese. A manganese amino-alkoxide compound represented by the formula 1 is prepared by reacting manganese oxide represented by the formula 3 and amino alcohol compound represented by the formula 4. In the formula 1 and 4, A shows a linear or branched C2-C10 alkylene, which is substituted or non-substituted with halogen; and R^1 and R^2 are independently linear or branched C1-C7 alkyl, which are substituted or non-substituted with halogen.

Description

Novel manganese amino-alkoxide complexes and process for preparing knowledge

The present invention relates to a novel manganese aminoalkoxide compound, and more particularly, precursors for manganese and manganese oxide thin film and precursors for preparing nano-sized manganese and manganese oxide particles, and LiAlMnO ₄ , LiCoMnO ₄ (lithium 2 Lithium-manganese oxide for secondary batteries), La _x Ca _y MnO ₃ (Manufacture of magnetic cooling engine), Mn / Ga alloy (magnetic-optical memory), and manganese aminoalkoxide compounds useful as precursors for the production of alloys and nanomaterials including manganese, and methods for producing the same.

Manganese oxides in various forms such as MnO, Mn ₃ O ₄ , Mn ₂ O ₃ , and MnO ₂ are used for the production of electrode materials, electrochemical capacitors, and soft magnetic materials. Can be. Manganese oxide is also used as a substrate to synthesize metal oxide perovskite compounds with various electrical and magnetic properties such as colossal magnetoresistance and metal-insulater transitions ( Dakhel, AA Thin Solid Films. 2006 , 496, 353; Nilsen, O .; Fjellvag, H .; Kjekshus, A. Thin Solid Films . 2003 , 444, 44; Nardi, JCZ J. Electrochem . Soc . 1985 , 132, 1787; Reddy, RN; Reddy, GR J. Power Sources 2004 , 132, 315; Shao, C .; Guan, H; Liu, Y .; Li, X .; Yang, X. J. Solid State Chem . 2004 , 177, 2628; Rao, CNR; Cheetham, AK Adv . Mater . 1997 , 9, 1009; Kim, KJ; Park, YR J. Cryst . Growth 2004 , 270, 162; Regulski, M .; Prezenioslo, I .; Hohlwein, D. Schneider, RS J. Alloys Compd . 2004 , 362, 236). In particular, MnO ₂ exhibits electrochromic properties and is used as a catalyst for oxidation of hydrocarbons, oxidation and reduction of nitrogen oxides, and decomposition of ozone, and most of all in batteries (Craciun, N .; Dulamita, N. Catal). Lett. 1997, 46, 229; Chem, L .; Horiuchi, T .; Mori, T. Catal . Lett . 1999 , 60, 237; Oyama, ST Catal. Rev.-Sci. Eng. 2000, 42, 279. ; garnich, F .; Yu PC; .. Lampert, CM Sol Energy Mater . 1990 , 20, 265; Cordoba de Torresi, SI; Gorenstein, A. Electrochim . Acta 1992 , 37, 2015; Yosida, A .; Nishino, A. J. Electrochem . Soc . 1989 , 136, 1896).

Methods for producing manganese oxide include solution phase chemical processes such as anodic oxidation, electrodeposition, electrolytic deposition, spray-pyrolysis, and electron beam evaporation, chemistry. It is mainly manufactured by chemical vapor deposition (CVD), sputtering, molecular beam epitaxy, pulsed laser deposition, etc., and is currently manufactured by atomic layer deposition, ALD) (Ord, JL; Huang, ZQ J. Electrochem . Soc . 1985 , 132, 1183; Mindt, W. Electrochem . Soc . 1971 , 118, 93; Rizzi, GA; Zanoni, R .; Di Siro, S .; Perriello, L .; Granozzi, G. Surf Sci 2000, 462, 187;.. Guo, LW; Makino, H .; Ko, HJ; Chen, YF; Hanada, T .; Peng, DL ; Inaba, K .; Yao, T. J. Cryst Growth 2001, 227, 955;. Neubeck, W .; Ranno, L .; Hunt, MB;.. Vettier, C .; Givord, D. Appl Surf Sci. 1999 , 138, 195).

The precursors used to prepare manganese, manganese oxide, and manganese-containing materials by the above-mentioned methods include Mn (thd) ₃ (thd = 2,2,6,6, -tetramethyl-3,5-heptanedionate ), Manganese oxalate and the like are known. The use of these precursors results in undesired reactions in the gas phase, contamination by carbon or halogens, low thermal stability, low vapor pressure, deposition only at high temperatures, low purity of the deposited film and poor surface quality. (Nakamura, T .; Tai, R .; Nishimura, T .; Tachibana, K. J. Electrochem . Soc ., 2005, 152, C584; Nilsen, O .; Fjellvag, H .; Kjekshus, A. Thin Solid Films . 2003 , 444, 44; Ahmad, T .; Ramanujachary, KV; Lofland, SE; Ganguli, AK J. M ater. C hem. , 2 0 0 4, 1 4, 3 4 0 6; Bessergenev, VG; Pereira, RJF; Botelho do Rego, AM Surface & Coatings Technology 2007, 201, 9141).

The present inventors introduced a new ligand to coordinate the dialkylamino group in manganese, which does not cause contamination of carbon or halogen, improves thermal stability and volatility, and easily includes manganese and manganese oxide, and manganese at lower temperatures. It has led to the development of new manganese precursors for the preparation of.

An object of the present invention is to provide high quality manganese and manganese oxide thin films and nanoparticles, and LiAlMnO ₄ , LiCoMnO ₄ , La _x Ca _y MnO ₃ , Mn / Ga The present invention provides a novel manganese compound precursor that is thermally stable and has increased volatility to form a compound including manganese, and the like, and a method of preparing the same.

The present invention provides a manganese aminoalkoxide compound represented by the following formula (1) to achieve the above object.

[Formula 1]

[Wherein A is a linear or branched C 2 -C 10 alkylene which is optionally substituted with halogen; R ¹ and R ² are, independently from each other, C 1 -C 7 linear or branched alkyl, optionally substituted with halogen.]

More specifically, the manganese aminoalkoxide compound of Formula 1 includes a manganese aminoalkoxide compound represented by Formula 2 below.

[Formula 2]

[Wherein m is 1 to 3; R ¹ and R ² are, independently from each other, C 1 -C 5 linear or branched alkyl, optionally substituted with fluorine; R ³ and R ⁴ independently of one another are linear or branched C1-C5 alkyl, optionally substituted with hydrogen or fluorine.]

In particular, a manganese aminoalkoxide compound having m of 1 or 2 in Formula 2 is preferable, and specifically, in Formula 2, R ¹ and R ² independently of each other are CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) Is selected from ₂ and C (CH ₃ ) ₃ , R ³ and R ⁴ are independently selected from hydrogen, CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ Illustrative manganese aminoalkoxide compounds are illustrated.

Hereinafter, the present invention will be described in more detail.

The manganese aminoalkoxide compound of formula 1 according to the present invention may be prepared by reacting a manganese compound of formula 3 with two equivalents of an amino alcohol compound of formula 4 in an inert argon or nitrogen atmosphere.

[Formula 1]

[Formula 3]

[Formula 4]

[In Formula 1 and Formula 4, A is a linear or branched C 2 -C 10 alkylene which is optionally substituted with halogen; R ¹ and R ² are, independently from each other, C 1 -C 7 linear or branched alkyl, optionally substituted with halogen.]

The compound of formula 1 as a reaction product was identified using Fourier transform infrared spectroscopy (FT-IR) [FIG. 1 and FIG. 2] and elemental analysis (EA). The manganese (II) aminoalkoxide compound, which is the organic manganese divalent compound thus prepared, is a white solid at room temperature, and some compounds are not soluble in organic solvents, but R ³ of formula (2) And when R ⁴ is asymmetrically substituted, it is well soluble in an organic solvent.

The thermal stability, volatility and decomposition temperature of the manganese compounds synthesized in the present invention were analyzed using thermogravimetric analysis / differential thermal analysis (TGA / DTA). As shown in FIG. 3, in the case of the (dimethylamino-2-methyl-2-propoxy) manganese (II) [Mn (dmamp) ₂ ] compound, it can be seen that a sharp mass decrease occurs between 293 and 329 ° C. .

Using a manganese aminoalkoxide compound of Formula 1 as a precursor, a thin film of manganese and manganese oxide, a nanoparticle of manganese and manganese oxide, or a dissimilar metal compound including manganese by a conventional method such as metal organic chemical vapor deposition (MOCVD) The manganese compound of can be manufactured.

As described above, the manganese aminoalkoxide compound of the present invention does not cause contamination of carbon or halogen by coordinating a dialkyl amino group to manganese, and exhibits excellent thermal stability and improved volatility, thereby reducing manganese and manganese oxide nanoparticles at low temperatures, In addition, there is an effect that can be usefully used as a precursor that can produce a compound containing manganese, such as manganese alloy.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

EXAMPLE

All experiments were performed in an inert argon or nitrogen atmosphere using a glove box or Schlenk line. The structure and properties of the reaction product were analyzed using Fourier infrared spectroscopy (FT-IR), elemental analysis (EA) and thermogravimetric analysis / differential thermal analysis (TGA / DTA). .

[ Example  1] (dimethylamino-2- methyl -2- Propoxy ) Manganese ( II ) [Mn ( dmamp ) ₂ Synthesis

Tetra hydrofuran (THF, 20 mL) was added to a 100 mL Schlenk flask, followed by Mn [N {Si (CH ₃ ) ₃ } ₂ ] ₂ (1.87 g, 5 mmol) and dimethylamino-2-methyl-2-propanol ( dmampH, 1.17 g, 10 mmol) were added and stirred for 3 hours. The mixed solution was filtered to separate Mn (dmamp) ₂ , the title compound, as a white solid.

Yield: 1.25 g (87%)

Elemental Analysis C ₁₂ H ₂₈ N ₂ O ₂ Mn (dmamp) ₂ H ₂ O {calculated (calculated)}: C, 49.08 (49.30); H, 10.75 (11.55); N, 9.54 (9.55).

FT-IR (cm ⁻¹ , KBr pellet): υ (MO) 541 cm ⁻¹ .

[ Example  2] (dimethylamino-2- methyl -2- Butoxy ) Manganese ( II ) [Mn ( dmamb ) ₂ Synthesis

Add tetrahydrofuran (THF, 20 mL) to a 100 mL Schlenk flask and add Mn [N {Si (CH ₃ ) ₃ } ₂ ] ₂ (1.87 g, 5 mmol) and dimethylamino-2-methyl-2-butanol ( dmambH, 1.31 g, 10 mmol) were added respectively and stirred for 3 hours. The mixed solution was filtered and the filtrate was dried in vacuo to separate the title compound Mn (dmamb) ₂ as a white solid.

Yield: 1.40 g (89%)

Elemental Analysis C ₁₄ H ₃₂ N ₂ O ₂ MnH ₂ O {calculated (calculated)}: C, 50.44 (50.41); H, 10.28 (10.19); N, 8.40 (8.99).

FT-IR (cm ⁻¹ , KBr pellet): υ (MO) 524, 592 cm ⁻¹ .

1 is a result of Fourier transform infrared spectroscopy (FTIR) analysis of a Mn (dmamp) ₂ compound prepared in Example 1,

2 is a result of Fourier transform infrared spectroscopy (FTIR) analysis of the Mn (dmamb) ₂ compound prepared in Example 2,

3 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the Mn (dmamp) ₂ compound prepared in Example 1.

Claims (7)

Manganese aminoalkoxide compound represented by the following formula (1). [Formula 1]

[Wherein A is a linear or branched C 2 -C 10 alkylene which is optionally substituted with halogen; R ¹ and R ² are, independently from each other, C 1 -C 7 linear or branched alkyl, optionally substituted with halogen.] The method of claim 1, Manganese aminoalkoxide compounds represented by the following formula (2). [Formula 2]

[Wherein m is 1 to 3; R ¹ and R ² are, independently from each other, C 1 -C 5 linear or branched alkyl, optionally substituted with fluorine; R ³ and R ⁴ independently of one another are linear or branched C1-C5 alkyl, optionally substituted with hydrogen or fluorine.] The method of claim 2, Manganese aminoalkoxide compound, characterized in that m is 1 or 2 in the formula (2). The method of claim 3, wherein Wherein R ¹ and R ² are each independently selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ³ and R ⁴ are independently hydrogen, A manganese aminoalkoxide compound, characterized in that it is selected from CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ . A method for preparing a manganese aminoalkoxide compound of formula (1), comprising reacting a manganese compound of formula (3) with an amino alcohol compound of formula (4). [Formula 1]

[Formula 3]

[Formula 4]

[In Formula 1 and Formula 4, A is a linear or branched C 2 -C 10 alkylene which is optionally substituted with halogen; R ¹ and R ² are, independently from each other, C 1 -C 7 linear or branched alkyl, optionally substituted with halogen.] A method for preparing a manganese compound using the manganese aminoalkoxide compound according to any one of claims 1 to 4 as a precursor. The method of claim 6, The manganese compound is a method for producing a manganese compound, characterized in that the thin film of manganese and manganese oxide, nanoparticles of manganese and manganese oxide or a heterometal compound containing manganese.

Images