JPS6284093A - Group v metal ethane dithiolate complex and production thereof - Google Patents

Abstract

NEW MATERIAL:A complex expressed by the formula [(C6H5)4P][M(S2C2H4)3] (M is niobium or tantalum). EXAMPLE:[(C6H5)4P][Nb(S2C2H4)3]. USE:A raw material for producing a Group V metal chalcogenide which is an inorganic high polymer. PREPARATION:A metal pentahalide expressed by the formula MX5<1> (X<1> is halogen), e.g. niobium pentachloride, is reacted with a lithium salt of ethanedithiol expressed by the formula LiSCH2CH2SLi and a tetraphenylphosphonium halide expressed by the formula (C6H5)4PX<2> (X<2> is halogen), e.g. tetraphenylphosphonium chloride, in the presence of acetonitrile.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a group V metal ethanedithiolate complex and a method for producing the same.
The present invention relates to a group metal ethanedithiolate complex and an efficient method for producing the same.

[Prior art and problems to be solved by the invention] Chalcogenide compounds of Group I metals of the periodic table, such as niobium and tantalum, are inorganic polymer compounds that exhibit interesting physical properties such as unique electromagnetic properties. It is attracting attention in various fields.

However, to date, the method for producing the above-mentioned inorganic polymer compounds has been limited to a method in which a mixture of Group 1 metal powder and chalcogen is subjected to a solid phase reaction at a high temperature of 500 to 1000°C. Moreover, the inorganic polymer compounds obtained by this solid-phase reaction do not necessarily exhibit desired physical properties, and it has been difficult to produce ones with practical value.

Therefore, the present inventors have conducted intensive research in order to solve the drawbacks of the above-mentioned solid-phase reaction method and to efficiently produce group V metal chalcogenide, which is an inorganic polymer compound with excellent physical properties, using a completely new method. layered.

As a result, by employing a new method of complex chemistry and thermally decomposing a specific group V metal complex, we succeeded in producing a group V metal chalcogenide having the desired physical properties. In addition, in the course of the research, the present inventors also succeeded in developing a completely new complex as the above-mentioned group Ⅰ metal complex as a raw material for thermal decomposition.

The purpose of the present invention is to provide a novel group V metal complex useful as a raw material for producing group V metal chalcogenide, which is an inorganic polymer compound having excellent physical properties, and to provide an effective method for producing this complex. be.

[Means for solving problems]

That is, the present invention provides a group II metal ethanedithiolate complex represented by the general formula % (in the formula, M represents niobium or tantalum); As a method for producing the Group V metal ethanedithiolate complex represented by the general formula M
Metal pentahalide 9 formula L represented by X's (wherein, XI represents a halogen atom, and M is the same as above)
i S G Hz CH! Lithium salt of ethanedithiol represented by S and general formula (CiHs) aPX”
(In the formula, X2 represents a halogen atom.) A method of reacting a halogenated tetraphenylphosphonium represented by , X' is the same as above) and a metal pentahalide represented by the formula L
The lithium salt of ethanedithiol represented by i S CHz CHz S Li is reacted in the presence of an inert hydrocarbon solvent, and then tetrahydrofuran is added to the resulting reaction product to obtain the general formula [Li (thf), )( M (SzCtH4)3)(
In the formula, (thf) represents tetrahydrofuran, and M is the same as above. ), and then reacting the complex with a tetraphenylphosphonium halide represented by the general formula (CiHs) 2).

Specifically, the group V metal ethanedithiolate complex of the present invention represented by the above general formula (1) is represented by the formula ((C4H6)
JP) (Nb(S,C,HJ)!) or the formula ((CiHs)4
A tantalum ethanedithiolate complex represented by P)CTa(SzCzHa)3) can be mentioned.

In order to produce the above Group Ⅰ metal ethanedithiolate complex by the method 1 of the present invention described above, a metal pentahalide,
The lithium salt of ethanedithiol and the tetraphenylphosphonium halide may be reacted in the presence of acetonitrile. Here, the metal pentahalide has the general formula MXI
, specifically niobium pentachloride (
NbCIS).

Tantalum pentachloride (TaC1s), niobium pentabromide (NbB
rs).

Examples include tantalum pentabromide (TaBrs).

The lithium salt of ethanedithiol is sulfonium, which is represented by the general formula (CiHs)aPX2, but specifically, tetraphenylphosphonium chloride ((
C6H5)4Pcl), tetraphenylphosphonium bromide ((C6H%)4PBr), and the like.

In method 1 of the present invention, each of the above-mentioned compounds may be reacted in the presence of acetonitrile, and there is no particular restriction on the reaction order, but preferably, the metal pentahalide and the lithium salt of ethanedithiol are first reacted. The reaction is carried out in acetonitrile and the reaction product is then reacted with tetraphenylphosphonium halide in acetonitrile. Further, the reaction temperature at this time is not particularly limited and may be selected as appropriate, but generally the reaction may be allowed to proceed within a range of about -40°C to 50°C, preferably about 0°C to 20°C.

On the other hand, in order to produce a group (III) metal ethanedithiolate complex by method 2 of the present invention, first, the aforementioned metal pentahalide and lithium salt of ethanedithiol are mixed in an inert hydrocarbon solvent such as benzene, toluene, or xylene. react in the presence of Next, when tetrahydrofuran is added to the product of this reaction, it has the formula [Li (thf)s ) (Nb(
SzCz)I4):+ ) and the formula [Li (thf)z
] (Ta(SzCzHa)3) A lithium-containing complex is obtained. Further, by reacting this lithium-containing complex with the above-mentioned tetraphenylphosphonium halide, the desired group (1) metal ethanedithiolate complex can be obtained. Here, the reaction between the lithium-containing complex and the tetraphenylphosphonium halide is preferably carried out in a solvent such as acetonitrile, and the series of reactions in method 2 above proceed under various temperature conditions; Usually -40℃ to 50℃, preferably θ℃ to 20℃
You can set it within the range.

According to the above-mentioned method 1 or method 2, a crystal of the group V metal ethanedithiolate complex represented by the general formula (1) is obtained, but this crystal is further mixed with dimethylformamide CD
If the complex is dissolved in a solvent such as MP) and recrystallized, a complex with even higher purity can be obtained.

〔Effect of the invention〕

According to Methods 1 and 2 of the present invention, group Ⅰ metal ethanedithiolate complexes can be obtained with high yield and high purity. Also,
Through a simple thermal decomposition reaction, this group V metal ethanedithiolate complex becomes an inorganic polymer compound with good electrical conductivity called a group V metal i chalcogenide such as niobium chalcogenide or tank chalcogenide.

Therefore, the Group 1 metal ethanedithiolate complex of the present invention can be effectively used as a raw material for producing an inorganic polymer compound exhibiting good electrical conductivity.

〔Example〕

Example 1 Preparation of obethane dithiolate complex) 6.8 g (25 mmol) of niobium pentachloride (NbC1s) was dissolved in 50 IIIt of acetonitrile to prepare a niobium pentachloride solution. On the other hand, 8.2 g of lithium salt of ethanedithiol [LiS CHtCHas Lt]
A suspension of 77 mmol) in 80 ml of acetonitrile was stirred in a 0°C water bath, and the niobium pentachloride solution was added little by little thereto. The reaction occurred immediately, resulting in a red solution, which was left to stir for 1 hour. Next, after removing impurities by decantation and filtration, approx.
/3 volume of solvent was distilled off.

Thereafter, 9.6 g of tetraphenylphosphonium bromide ((CaHs)nP Br) (23
When a solution of 1 mmol) dissolved in 40 ml of acetonitrile was added little by little, crystals began to precipitate after about 1 minute. - After standing in the refrigerator overnight, the crude crystals were collected by filtration.

The yield of crude crystals was 13.6 g, giving a yield of 77%.

Subsequently, 1.4 g of the above crude crystals were taken, dissolved in 40 val of dimethylformamide (DMF), and filtered. About 1/2 volume of DMF was distilled off, and the mixture was left standing in a refrigerator overnight. The next day, after drawing out the solution with a syringe and washing the crystals with a small amount of acetonitrile and diethyl ether,
Dry under reduced pressure for an hour.

As a result, 1.2 g of purified crystals (yield: 86%) were obtained. The analysis results for this item are as follows: Elemental analysis values (%) Carbon Hydrogen Nitrogen Sulfur Calculated values 50.68 5.04 1.79 24.6
0 Actual value 50.61 4.95 1.84 24.
75((C,Hs)4P)(Nb(SgCgHn)J)
・DMF.

Composition formula: NbC-azHsqN OP Sh proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d6
).

63.66 (SCHz 12H, s).

7.84 ((Ci, Hs) aP 20H, m).

2.82 (DMF Cdan 3 6H, a).

8.04 (DMF I H, 5br) far infrared absorption spectrum (Nujol IIIull) 440w,
354m, 331n (am-') Ultraviolet-visible light absorption spectrum (CHffCN) λ, nm (
10-'t, M-'ell-') 523 (0,4
8) 386 (1,02), 325 (1,14) Example 2 Production of obethane dithiolar Hf form) 6.2 g (23 mmol) of niobium pentachloride (NbC1s) was suspended in benzene 100111, The lithium salt of ethanedithiol [LiS] was added to this while stirring in a water bath at 0°C.
7.5 g (71 mmol) of CHzCHisLi) was added little by little as a powder. After distilling off the benzene, the remaining reddish brown solid was treated with tetrahydrofuran (TH
When F) was poured, it became a red solution in about 10 minutes. When this was filtered and subjected to tlA condensation, red crystals were obtained. Yield is 5
．． 9 g, yield was 43% (based on NbC1s). In addition, this red crystal has the formula [Li (thf)s ) (Nb (SgCgHn) +
) was found to be a lithium-containing complex represented by
It was.

Subsequently, 2.5 g (4.2 mmol) of this lithium-containing complex was dissolved in 35 all acetonitrile, and a solution of 1.76 g (4.2 mmol) of tetraphenylphosphonium bromide in 30n+1 acetonitrile was added thereto. As a result, crystals were produced, and the yield was 2.7 g, 90%.

When this crystal was analyzed in the same manner as in Reference Example 1, it was found that it had the formula ((C4H6)4P)(Nb(SgCgHn))
It was confirmed that it is a niobium ethanedithiolate complex represented by

Example 3 (Production of tantalum ethanedithiolate complex)
In Example 1, 4.0 g (11.8 mmol) of tantalum pentachloride (1 g of TaC) was used instead of niobium pentachloride.
The same operation as in Example 1 was performed except that 7.2 g of crystals were obtained in a yield of 77%. The analysis results of this product were as follows.

Elemental analysis value (%) Carbon Hydrogen Nitrogen Sulfur calculation value 45.55 4,53 1.61 22.1
1 Actual value 45.31 4.49 1.64 22.
00((C6H3)JP)(Ta(SgCgHn)z
)・DMF.

Compositional formula: TaC3sH**N0PS6 Proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d6).

δ3.87 (SC-Ll 2)(,s),'
7.85 ((C & 5) 4P 20 H, m).

2.82 (DMF C and 3 6H, d).

8.05 (DMF I H, 5br) far infrared absorption spectrum (Nujol mall) 442w,
333m, 307m (cm-') Ultraviolet-visible absorption spectrum (CH3CN) λ, nm (10”
'a, M-'cffi-') 441 (0,62)
.

Claims (3)

[Claims] (1) General formula [(C_6H_5)_4P] [M(S_2C_2H_4
)_3] (In the formula, M represents niobium or tantalum.) A Group V metal ethanedithiolate complex. (2) Metal pentahalides represented by the general formula MX^1_5 (wherein M represents niobium or tantalum, and X^1 represents a halogen atom), lithium salts of ethanedithiol represented by the formula LiSCH_2CH_2SLi, and general Formula (C_6H_5)_
General formula [(C_6H_5)_4P] [M(S_2C_2H
_4)_3] (wherein M is the same as above) A method for producing a group V metal ethanedithiolate complex. (3) A metal pentahalide represented by the general formula MX^1_5 (wherein M represents niobium or tantalum, and X^1 represents a halogen atom) and a lithium salt of ethanedithiol represented by the formula LiSCH_2CH_2SLi are unused. The reaction is carried out in the presence of an activated hydrocarbon solvent, and then tetrahydrofuran is added to the resulting reaction product to obtain the general formula [Li(thf)_3][M(S_2C_2H_4)_
3] (wherein (thf) represents tetrahydrofuran,
M is the same as above. ) is obtained, and then the complex is converted into a lithium-containing complex represented by the general formula (C_6H_5)_
General formula [(C_6H_5)_4P] [M(S_2C_2H_4
)_3] (In the formula, M is the same as above.) A method for producing a group V metal ethanedithiolate complex.