JPH0451557B2 - - Google Patents
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- Publication number
- JPH0451557B2 JPH0451557B2 JP22271885A JP22271885A JPH0451557B2 JP H0451557 B2 JPH0451557 B2 JP H0451557B2 JP 22271885 A JP22271885 A JP 22271885A JP 22271885 A JP22271885 A JP 22271885A JP H0451557 B2 JPH0451557 B2 JP H0451557B2
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- JP
- Japan
- Prior art keywords
- metal
- represented
- formula
- complex
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Chemical group 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- 238000000034 method Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 12
- -1 Chalcogenide compounds Chemical class 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229920000592 inorganic polymer Polymers 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000004770 chalcogenides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000761456 Nops Species 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＶ族金属エタンジチオラート錯体およ
びその製造方法に関し、詳しくは特定の式で表わ
される新規なＶ族金属エタンジチオラート錯体お
よびその効率のよい製造方法に関する。[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, and more particularly, to a novel group V metal ethanedithiolate complex represented by a specific formula and its efficiency. Concerning a good manufacturing method.
ニオブ、タンタル等の周期表第Ｖ族金属のカル
コゲニド化合物は、特有の電磁気的性質等、興味
深い物性を示す無機高分子化合物であり、最近
様々な分野で注目を浴びてきている。
Chalcogenide compounds of Group V metals of the periodic table, such as niobium and tantalum, are inorganic polymer compounds that exhibit interesting physical properties such as unique electromagnetic properties, and have recently attracted attention in various fields.
しかし、これまでのところ上述の無機高分子化
合物を製造するには、Ｖ族金属の粉末とカルコゲ
ンを混合したものを500〜1000℃の高温下で固相
反応させる方法に限られていた。しかも、この固
相反応によつて得られる無機高分子化合物は、必
ずしも所望する物性を示さず、実用的価値のある
ものはなかなか製造することができなかつた。 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 V 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.
そこで、本発明者らは、上述の固相反応による
方法の欠点を解消し、全く新たな方法で効率よく
しかも物性のすぐれた上記無機高分子化合物であ
るＶ族金属カルコゲニドを製造すべく鋭意研究を
重ねた。 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.
その結果、錯体化学的な新しい手法を採用し
て、特定のＶ族金属錯体を熱分解することによ
り、目的とする物性を有するＶ族金属カルコゲニ
ドを製造することに成功した。また、その研究過
程において、本発明者らは上述の熱分解原料とし
てのＶ族金属錯体として、全く新たな錯体を開発
することにも成功した。 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 group V metal complex used as the above-mentioned thermal decomposition raw material.
本発明の目的は、すぐれた物性を有する無機高
分子化合物たるＶ族金属カルコゲニドの製造原料
として有用な新規なＶ族金属錯体を提供するこ
と、およびこの錯体の有効な製造方法を提供する
ことにある。 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.
すなわち本発明は、
一般式
〔（C6H5）4Ｐ〕〔Ｍ（S2C2H4）3〕 …（）
（式中、Ｍはニオブあるいはタンタルを示す。）
で表わされるＶ族金属エタンジチオラート錯体を
提供するものであり、またこの一般式（）で表
わされるＶ族金属エタンジチオラート錯体を製造
する方法として、一般式MX1 5（式中、X1はハロ
ゲン原子を示し、Ｍは前記と同じである。で表わ
される五ハロゲン化金属、式 LiSCH2CH2SLi
で表わされるエタンジチオールのリチウム塩およ
び一般式（C6H5）4PX2（式中、X2はハロゲン原子
を示す。）で表わされるハロゲン化テトラフエニ
ルホスホニウムをアセトニトリルの存在下で反応
させる方法（以下「方法１」という。）、ならびに
一般式MX1 5（式中、Ｍ，X1は前記と同じ。）で
表わされる五ハロゲン化金属および式 LiSCH2
CH2SLiで表わされるエタンジチオールのリチウ
ム塩を不活性炭化水素溶媒の存在下で反応させ、
次いで得られた反応生成物にテトラヒドロフラン
を加えて一般式
〔Li（thf）3〕〔Ｍ（S2C2H4）3〕（式中、（thf）は
テトラヒドロフランを示し、Ｍは前記と同じであ
る。）で表わされるリチウム含有錯体を得、しか
る後に該錯体を一般式（C6H5）4PX2（式中、X2は
前記と同じ。）で表わされるハロゲン化テトラフ
エニルホスホニウムと反応させる方法（以下「方
法２」という。）を提供するものである。
That is, the present invention has the following formula: [(C 6 H 5 ) 4 P] [M(S 2 C 2 H 4 ) 3 ]...() (In the formula, M represents niobium or tantalum.)
The purpose of the present invention is to provide a group V metal ethanedithiolate complex represented by the general formula (MX 1 5 represents a halogen atom, and M is the same as above.Metal pentahalide represented by, formula LiSCH 2 CH 2 SLi
A lithium salt of ethanedithiol represented by ethanedithiol and a halogenated tetraphenylphosphonium represented by the general formula (C 6 H 5 ) 4 PX 2 (wherein, X 2 represents a halogen atom) are reacted in the presence of acetonitrile. method (hereinafter referred to as "Method 1"), and a metal pentahalide represented by the general formula MX 1 5 (wherein M and X 1 are the same as above) and the formula LiSCH 2
Reacting the lithium salt of ethanedithiol, represented by CH 2 SLi, in the presence of an inert hydrocarbon solvent,
Next, tetrahydrofuran was added to the obtained reaction product to obtain the general formula [Li(thf) 3 ][M(S 2 C 2 H 4 ) 3 ] (wherein (thf) represents tetrahydrofuran, and M is the same as above. A lithium-containing complex represented by the formula (C 6 H 5 ) 4 PX 2 (wherein , (hereinafter referred to as "Method 2").
前記一般式（）で表わされる本発明のＶ族金
属エタンジチオラート錯体は、具体的には
式〔（C6H5）4Ｐ〕〔Nb（S2C2H4）3〕で表わされ
るニオブエタンジチオラート錯体あるいは式
〔（C6H5）4Ｐ〕〔Ta（S2C2H4）3〕で表わされるタン
タルエタジチオラート錯体をあげることができ
る。 The Group V metal ethanedithiolate complex of the present invention represented by the general formula () is specifically represented by the formula [(C 6 H 5 ) 4 P] [Nb(S 2 C 2 H 4 ) 3 ] Examples include niobium ethadithiolate complexes and tantalum ethadithiolate complexes represented by the formula [(C 6 H 5 ) 4 P] [Ta(S 2 C 2 H 4 ) 3 ].
前述した本発明の方法１によつて、上記Ｖ族金
属エタンジチオラート錯体を製造するには、五ハ
ロゲン化金属、エタンジチオールのリチウム塩お
よびハロゲン化テトラフエニルホスホニウムをア
セトニトリルの存在下で反応させればよい。ここ
で五ハロゲン化金属は一般式MX1 5で表わされる
ものであり、具体的には五塩化ニオブ（NbCl5），
五塩化タンタル（TaCl5），五臭化ニオブ
（NbBr5），五臭化タンタル（TaBr5）などがあげ
られる。 In order to produce the Group V metal ethanedithiolate complex by the method 1 of the present invention described above, a metal pentahalide, a lithium salt of ethanedithiol, and a tetraphenylphosphonium halide are reacted in the presence of acetonitrile. That's fine. Here, the metal pentahalide is represented by the general formula MX 1 5 , and specifically, niobium pentachloride (NbCl 5 ),
Examples include tantalum pentachloride (TaCl 5 ), niobium pentabromide (NbBr 5 ), and tantalum pentabromide (TaBr 5 ).
またエタンジチオールのリチウム塩は
式 LiSCH2CH2SLiで表わされるジリチウム
塩である。さらに、ハロゲン化テトラフエニルホ
スホニウムは、一般式（C6H5）4PX2で表わされ
るが、具体的には塩化テトラフエニルホスホニウ
ム（（C6H5）4PCl），臭化テトラフエニルホスホニ
ウム（（C6H5）4PBr）などがあげられる。本発明
の方法１では、上記の各化合物をアセトニトリル
の存在下で反応させればよく、その反応順序等に
ついては特に制限はないが、好ましくはまず五ハ
ロゲン化金属とエタンジチオールのリチウム塩と
をアセトニトリル中で反応させ、次いでこの反応
生成物をアセトニトリル中でハロゲン化テトラフ
エニルホスホニウムと反応させる。また、この際
の反応温度についても特に制限はなく適宜選定す
ればよいが、一般に−40℃〜50℃、好ましくは０
℃〜20℃程度の範囲で反応を進行させればよい。The lithium salt of ethanedithiol is a dilithium salt represented by the formula LiSCH 2 CH 2 SLi. Furthermore, halogenated tetraphenylphosphonium is represented by the general formula (C 6 H 5 ) 4 PX 2 , but specifically tetraphenylphosphonium chloride ((C 6 H 5 ) 4 PCl), tetraphenyl bromide Examples include enylphosphonium ((C 6 H 5 ) 4 PBr). 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. The reaction temperature at this time is also not particularly limited and may be selected as appropriate, but is generally -40°C to 50°C, preferably 0°C.
The reaction may be allowed to proceed in the range of about ℃ to 20℃.
一方、本発明の方法２によつて、Ｖ族金属エタ
ンジチオラート錯体を製造するには、まず前述の
五ハロゲン化金属とエタンジチオールのリチウム
塩とをベンゼン，トルエン，キシレン等の不活性
炭化水素溶媒の存在下で反応させる。次に、この
反応の生成物にテトラヒドロフランを加えると、
式〔Li（thf）3〕〔Nb（S2C2H4）3〕や式〔Li（thf）3
〕
〔Ta（S2C2H4）3〕で表わされるリチウム含有錯体
が得られる。さらに、このリチウム含有錯体を前
述のハロゲン化テトラフエニルホスホニウムと反
応させれば目的とするＶ族金属エタンジチオラー
ト錯体が得られる。ここで、リチウム含有錯体と
ハロゲン化テトラフエニルホスホニウムを反応さ
せるにあたつては、アセトニトリル等の溶媒中で
行なうことが好ましい。また、上記方法２の一連
の反応は、様々な温度条件下で進行するが、通常
は−40℃〜50℃、好ましくは０℃〜20℃の範囲に
設定すればよい。 On the other hand, in order to produce a group V metal ethanedithiolate complex by method 2 of the present invention, first, the aforementioned metal pentahalide and lithium salt of ethanedithiol are mixed with an inert hydrocarbon such as benzene, toluene, or xylene. React in the presence of a solvent. Then, when tetrahydrofuran is added to the product of this reaction,
Formula [Li(thf) 3 ][Nb(S 2 C 2 H 4 ) 3 ] or formula [Li(thf) 3]
]
A lithium-containing complex represented by [Ta(S 2 C 2 H 4 ) 3 ] is obtained. Furthermore, by reacting this lithium-containing complex with the aforementioned tetraphenylphosphonium halide, the desired Group V 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. Further, the series of reactions in Method 2 above proceed under various temperature conditions, but usually the temperature may be set in the range of -40°C to 50°C, preferably 0°C to 20°C.
上述の方法１あるいは方法２によれば、一般式
（）で表わされるＶ族金属エタンジチオラート
錯体の結晶が得られるが、さらにこの結晶をジメ
チルホルムアミド（DMF）等の溶媒に溶解し、
再結晶を行なえば一層純度の高い錯体が得られ
る。 According to the above-mentioned method 1 or method 2, a crystal of a group V metal ethanedithiolate complex represented by the general formula () is obtained, but this crystal is further dissolved in a solvent such as dimethylformamide (DMF),
A more pure complex can be obtained by recrystallization.
本発明の方法１，２によれば、高い収率でしか
も高純度のＶ族金属エタンジチオラート錯体が得
られる。また、このＶ族金属エタンジチオラート
錯体は、簡単な熱分解反応によつて、ニオブカル
コゲニドやタンタルカルコゲニドのＶ族金属カル
コゲニドと称される電気伝導性の良好な無機高分
子化合物となる。
According to Methods 1 and 2 of the present invention, group V metal ethanedithiolate complexes can be obtained with high yield and high purity. Further, this group V metal ethanedithiolate complex becomes an inorganic polymer compound with good electrical conductivity called a group V metal chalcogenide such as niobium chalcogenide or tantalum chalcogenide through a simple thermal decomposition reaction.
したがつて、本発明のＶ族金属エタンジチオラ
ート錯体は、良好な電気伝導性を示す無機高分子
化合物の製造原料として有効に利用することがで
きる。 Therefore, the group V 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.
実施例 １
（ニオブエタンジチオラート錯体の製造）
五塩化ニオブ（NbCl5）6.8g（25ミリモル）を
アセトニトリル50mlに溶かして五塩化ニオブ溶液
を調製した。一方、エタンジチオールのリチウム
塩（LiSCH2CH2SLi）8.2g（77ミリモル）をアセ
トニトリル80mlに懸濁した懸濁液を、０℃氷浴中
で攪拌し、ここへ前記五塩化ニオブ溶液を少量ず
つ添加した。反応は直ちに起こり、赤色溶液とな
つたが、そのまま１時間攪拌した。次に、デカン
テーシヨンと濾過によつて不純物を除去した後、
約1/3体積の溶媒を留去した。
Example 1 (Production of niobium ethanedithiolate complex) A niobium pentachloride solution was prepared by dissolving 6.8 g (25 mmol) of niobium pentachloride (NbCl 5 ) in 50 ml of acetonitrile. On the other hand, a suspension of 8.2 g (77 mmol) of lithium salt of ethanedithiol (LiSCH 2 CH 2 SLi) in 80 ml of acetonitrile was stirred in an ice bath at 0°C, and a small amount of the niobium pentachloride solution was added thereto. were added one by one. The reaction occurred immediately, resulting in a red solution, which was left to stir for 1 hour. Then, after removing impurities by decantation and filtration,
Approximately 1/3 volume of solvent was distilled off.
その後、得られた溶液に、臭化テトラフエニル
ホスホニウム（（C6H5）4PBr）9.6g（23ミリモル）
をアセトニトリル40mlに溶かした溶液を少量ずつ
加えたところ、約１分後に結晶が析出しはじめ
た。一晩、冷蔵庫に静置した後、粗結晶を濾取し
た。粗結晶の収量は13.6gであり、収率は77％で
あつた。 Then, 9.6 g (23 mmol) of tetraphenylphosphonium bromide ((C 6 H 5 ) 4 PBr) was added to the resulting solution.
When a solution prepared by dissolving . 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%.
続いて、上記粗結晶1.4gを採り、これをジメチ
ルホルムアミド（DMF）40mlに溶解されて濾過
した後、約1/2体積のDMFを留去し、冷蔵庫に一
晩静置した。翌日、溶液を注射器で吸出して結晶
を少量のアセトニトリルおよびジエチルエーテル
で洗浄した後、６時間減圧乾燥した。その結果精
製された結晶1.2g（収率86％）が得られた。この
ものの分析結果は次のとおりであつた。 Subsequently, 1.4 g of the above crude crystals were taken, dissolved in 40 ml 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, the solution was sucked out with a syringe, the crystals were washed with a small amount of acetonitrile and diethyl ether, and then dried under reduced pressure for 6 hours. As a result, 1.2 g of purified crystals (yield 86%) were obtained. The analysis results of this product were as follows.
元素分析値（％）
炭素 水素 窒素 硫黄
計算値 50.68 5.04 1.79 24.60
実測値 50.61 4.95 1.84 24.75
〔（C6H5）4Ｐ〕〔Nb（S2C2H4）3〕・DMF，組成
式：NbC33H39NOPS6
プロトン核磁気共鳴スペクトル（ジメチルスルホ
キシド−d6），
δ 3.66（SCH2 12H，ｓ），
7.84（（C6H5）4Ｐ 20H，ｍ），
2.82（DMF ＣH3 6H，ｄ），
8.04（DMF 1H，sbr）
遠赤外線吸収スペクトル（Nujol mull）
440w，354m，331m（cm-1）
紫外−可視光線吸収スペクトル（CH3CN）
λ，nm（10-4ε，M-1cm-1）523（0.48），386
（1.02），325（1.14）
実施例 ２
（ニオブエタンジチオラート錯体の製造）
五塩化ニオブ（NbCl5）6.2g（23ミリモル）を
ベンゼン100mlに懸濁させ、０℃の氷浴中で攪拌
しながら、これにエタンジチオールのリチウム塩
（LiSCH2CH2SLi）7.5g（71ミリモル）を粉末のま
ま少量ずつ加えた。ベンゼンを留去した後、残つ
た赤褐色の固体にテトラヒドロフラン（THF）
を注ぐと約10分で赤色の溶液になつた。これを濾
過し濃縮したところ赤色結晶が得られた。収量は
5.9g、収率は43％（NbCl5基準）であつた。また
この赤色結晶はプロトン核磁気共鳴スペクトル，
遠赤外線吸収スペクトル，紫外−可視光線吸収ス
ペクトルの分析結果から
式〔Li（thf）3〕〔Nb（S2C2H4）3〕で表わされる
リチウム含有錯体であることがわかつた。 Elemental analysis value (%) Carbon Hydrogen Nitrogen Sulfur Calculated value 50.68 5.04 1.79 24.60 Actual value 50.61 4.95 1.84 24.75 [(C 6 H 5 ) 4 P] [Nb (S 2 C 2 H 4 ) 3 ]・DMF, composition formula: NbC 33 H 39 NOPS 6 -proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d 6 ), δ 3.66 (SCH 2 12H, s), 7.84 ((C 6 H 5 ) 4 P 20H, m), 2.82 (DMF C H 3 6H, d), 8.04 (DMF 1H, sbr) Far-infrared absorption spectrum (Nujol mull) 440w, 354m, 331m (cm -1 ) Ultraviolet-visible absorption spectrum (CH 3 CN) λ, nm (10 -4 ε , M -1 cm -1 ) 523 (0.48), 386
(1.02), 325 (1.14) Example 2 (Production of niobium ethanedithiolate complex) 6.2 g (23 mmol) of niobium pentachloride (NbCl 5 ) was suspended in 100 ml of benzene and stirred in an ice bath at 0°C. Meanwhile, 7.5 g (71 mmol) of the lithium salt of ethanedithiol (LiSCH 2 CH 2 SLi) was added little by little as a powder. After distilling off the benzene, the remaining reddish brown solid is treated with tetrahydrofuran (THF).
When poured, it became a red solution in about 10 minutes. When this was filtered and concentrated, red crystals were obtained. The yield is
The yield was 43% (based on NbCl 5 ). This red crystal also has a proton nuclear magnetic resonance spectrum.
From the analysis results of far-infrared absorption spectrum and ultraviolet-visible light absorption spectrum, it was found to be a lithium-containing complex represented by the formula [Li(THF) 3 ][Nb(S 2 C 2 H 4 ) 3 ].
続いて、このリチウム含有錯体2.5g（4.2ミリモ
ル）をアセトニトリル35mlに溶かし、これに臭化
テトラフエニルホスホニウム1.76g（4.2ミリモル）
のアセトニトリル30ml溶液を添加した。その結
果、結晶が生成し、収量2.7g、収率約90％であつ
た。 Subsequently, 2.5 g (4.2 mmol) of this lithium-containing complex was dissolved in 35 ml of acetonitrile, and to this was added 1.76 g (4.2 mmol) of tetraphenylphosphonium bromide.
30 ml of acetonitrile solution was added. As a result, crystals were produced, and the yield was 2.7 g, about 90%.
この結晶を上記参考例１と同様の分析を行なつ
たところ、式〔（C6H5）4Ｐ〕〔Nb（S2C2H4）3〕で
表わされるニオブエタンジチオラート錯体である
ことが確認された。 When this crystal was analyzed in the same manner as in Reference Example 1 above, it was found to be a niobbutane dithiolate complex represented by the formula [(C 6 H 5 ) 4 P] [Nb(S 2 C 2 H 4 ) 3 ]. This was confirmed.
実施例 ３
（タンタルエタンジチオラート錯体の製造）
実施例１において五塩化ニオブの代わりに五塩
化タンタル（TaCl5）4.0g（11.8ミリモル）を用い
たこと以外は実施例１と同様の操作を行なつて結
晶を7.2g、収率77％にて得た。このものの分析結
果は次のとおりであつた。Example 3 (Production of tantalum ethanedithiolate complex) The same operation as in Example 1 was performed except that 4.0 g (11.8 mmol) of tantalum pentachloride (TaCl 5 ) was used instead of niobium pentachloride in Example 1. 7.2 g of crystals were obtained in a yield of 77%. The analysis results of this product were as follows.
元素分析値（％）
炭素 水素 窒素 硫黄
計算値 45.55 4.53 1.61 22.11
実測値 45.31 4.49 1.64 22.00
〔（C6H5）4Ｐ〕〔Ta（S2C2H4）3〕・DMF，組成
式：TaC33H39NOPS6
プロトン核磁気共鳴スペクトル（ジメチルスルホ
キシド−d6），
δ 3.87（SCH2 12H，ｓ），
7.85（C6H5）4Ｐ 20H，ｍ），
2.82（DMF ＣH3 6H，ｄ），
8.05（DMF 1H，sbr）
遠赤外線吸収スペクトル（Nujol mull）
442w，333m，307m（cm-1）
紫外−可視光線吸収スペクトル（CH3CN）
λ，nm（10-4ε，M-1cm-1）441（0.62），342
（1.28），291（1.64） Elemental analysis value (%) Carbon Hydrogen Nitrogen Sulfur Calculated value 45.55 4.53 1.61 22.11 Actual value 45.31 4.49 1.64 22.00 [(C 6 H 5 ) 4 P] [Ta (S 2 C 2 H 4 ) 3 ]・DMF, composition formula: TaC 33 H 39 NOPS 6 -proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d 6 ), δ 3.87 (SCH 2 12H, s), 7.85 (C 6 H 5 ) 4 P 20H, m), 2.82 (DMF C H 3 6H, d), 8.05 (DMF 1H, sbr) Far-infrared absorption spectrum (Nujol mull) 442w, 333m, 307m (cm -1 ) Ultraviolet-visible absorption spectrum (CH 3 CN) λ, nm (10 -4 ε, M -1 cm -1 ) 441 (0.62), 342
(1.28), 291 (1.64)
Claims (1)
で表わされるＶ族金属エタンジチオラート錯体。 ２ 一般式 MX1 5（式中、Ｍはニオブあるいは
タンタルを示し、X1はハロゲン原子を示す。）で
表わされる五ハロゲン化金属， 式 LiSCH2CH2SLiで表わされるエタンジチオ
ールのリチウム塩および一般式（C6H5）4PX2（式
中、X2はハロゲン原子を示す。）で表わされるハ
ロゲン化テトラフエニルホスホニウムをアセトニ
トリルの存在下で反応させることを特徴とする一
般式〔（C6H5）4Ｐ〕〔Ｍ（S2C2H4）3〕（式中、Ｍは
前記と同じ。）で表わされるＶ族金属エタンジチ
オラート錯体の製造方法。 ３ 一般式 MX1 5（式中、Ｍはニオブあるいは
タンタルを示し、X1はハロゲン原子を示す。）で
表わされる五ハロゲン化金属および 式 LiSCH2CH2SLiで表わされるエタンジチオ
ールのリチウム塩を不活性炭化水素溶媒の存在下
で反応させ、次いで得られた反応生成物にテトラ
ヒドロフランを加えて一般式 〔Li（thf）3〕〔Ｍ（S2C2H4）3〕（式中、（thf）は
テトラヒドロフランを示し、Ｍは前記と同じであ
る。）で表わされるリチウム含有錯体を得、しか
る後に該錯体を一般式（C6H5）4PX2（式中、X2は
ハロゲン原子を示す。）で表わされるハロゲン化
テトラフエニルホスホニウムと反応させることを
特徴とする一般式 〔（C6H5）4Ｐ〕〔Ｍ（S2C2H4）3〕 （式中、Ｍは前記と同じ。）で表わされるＶ族金
属エタンジチオラート錯体の製造方法。[Claims] 1 General formula [(C 6 H 5 ) 4 P] [M(S 2 C 2 H 4 ) 3 ] (In the formula, M represents niobium or tantalum.)
A group V metal ethanedithiolate complex represented by: 2 A metal pentahalide represented by the general formula MX 1 5 (wherein M represents niobium or tantalum and X 1 represents a halogen atom), a lithium salt of ethanedithiol represented by the formula LiSCH 2 CH 2 SLi, and General formula [ ( _ A method for producing a group V metal ethanedithiolate complex represented by C6H5) 4P ] [ M( S2C2H4 ) 3 ] (wherein M is the same as above). 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 2 CH 2 SLi. The reaction is carried out in the presence of an inert hydrocarbon solvent, and then tetrahydrofuran is added to the resulting reaction product to give the general formula [Li(thf) 3 ][M(S 2 C 2 H 4 ) 3 ] (in the formula, ( thf) represents tetrahydrofuran, and M is the same as above . General formula [(C 6 H 5 ) 4 P] [M(S 2 C 2 H 4 ) 3 ] (wherein, M is the same as above.) A method for producing a Group V metal ethanedithiolate complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22271885A JPS6284093A (en) | 1985-10-08 | 1985-10-08 | Group v metal ethane dithiolate complex and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22271885A JPS6284093A (en) | 1985-10-08 | 1985-10-08 | Group v metal ethane dithiolate complex and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6284093A JPS6284093A (en) | 1987-04-17 |
| JPH0451557B2 true JPH0451557B2 (en) | 1992-08-19 |
Family
ID=16786818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22271885A Granted JPS6284093A (en) | 1985-10-08 | 1985-10-08 | Group v metal ethane dithiolate complex and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6284093A (en) |
-
1985
- 1985-10-08 JP JP22271885A patent/JPS6284093A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6284093A (en) | 1987-04-17 |
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