JPS6284093A - Group v metal ethane dithiolate complex and production thereof - Google Patents
Group v metal ethane dithiolate complex and production thereofInfo
- Publication number
- JPS6284093A JPS6284093A JP22271885A JP22271885A JPS6284093A JP S6284093 A JPS6284093 A JP S6284093A JP 22271885 A JP22271885 A JP 22271885A JP 22271885 A JP22271885 A JP 22271885A JP S6284093 A JPS6284093 A JP S6284093A
- Authority
- JP
- Japan
- Prior art keywords
- complex
- metal
- formula
- group
- general formula
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- AHOQGTNJXHIEFO-UHFFFAOYSA-N S1SC(C=C1)C(=O)O.CC Chemical compound S1SC(C=C1)C(=O)O.CC AHOQGTNJXHIEFO-UHFFFAOYSA-N 0.000 title 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010955 niobium Substances 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052715 tantalum Chemical group 0.000 claims abstract description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 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 abstract description 37
- -1 tetraphenylphosphonium halide Chemical class 0.000 abstract description 11
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 abstract description 7
- 150000004770 chalcogenides Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 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 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 239000013078 crystal Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 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
- 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
- 238000000862 absorption spectrum Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000007787 solid Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 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
- 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 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
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、詳しくは特定の弐で表わされる新規な■
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.
The present invention relates to a group metal ethanedithiolate complex and an efficient method for producing the same.
〔従来の技術及び発明が解決しようとする問題点〕ニオ
ブ、タンタル等の周期表第■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。[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.
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、■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、この固相反応によって得られ
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
なかった。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 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.
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■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 above-mentioned group Ⅰ metal complex as a raw material for thermal decomposition.
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
％式％（）
（式中、Ｍはニオブあるいはタンタルを示す。）で表わ
される■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（Ｉ）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Ｍ
Ｘ’ｓ（式中、ＸＩ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９式Ｌ
ｉ Ｓ Ｇ Ｈｚ ＣＨ！ Ｓ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（ＣｉＨｓ）ａＰＸ”
（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ェ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ＭＸ’Ｓ（式中、Ｍ、Ｘ’は前記
と同じ。）で表わされる五ハロゲン化金属および式Ｌ
ｉ Ｓ ＣＨｚ ＣＨｚ Ｓ Ｌ ｉ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）、）（Ｍ （ＳｚＣｔＨ４）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（ＣｉＨｓ）＜ＰＸ”（式
中、Ｘｚは前記と同じ。）で表わされるハロゲン化テト
ラフェ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 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).
Ｌｉ前記一般式（１）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（（Ｃ４Ｈ６）
ＪＰ）（Ｎｂ（Ｓ、Ｃ，ＨＪ）！ ）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（（ＣｉＨｓ）４
Ｐ）ＣＴａ（ＳｚＣｚＨａ）３）で表わされるタンタル
エタンジチオラート錯体をあげることができる。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.
前述した本発明の方法１によって、上記■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
フェ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ＭＸＩ
、で表わされるものであり、具体的には五塩化ニオブ（
ＮｂＣＩＳ）。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).
五塩化タンタル（ＴａＣ１ｓ）、五臭化ニオブ（ＮｂＢ
ｒｓ）。Tantalum pentachloride (TaC1s), niobium pentabromide (NbB
rs).
五臭化タンタル（ＴａＢｒｓ）などがあげられる。Examples include tantalum pentabromide (TaBrs).
またエタンジチオールのリチウム塩は
スホニウムは、一般式（ＣｉＨｓ）ａＰＸ２で表わされ
るが、具体的には塩化テトラフェニルホスホニウム（（
Ｃ６Ｈ５）４Ｐｃｌ）、臭化テトラフェニルホスホニウ
ム（（Ｃ６Ｈ％）４ＰＢｒ）などがあげられる。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.
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ェ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、一般に一４０℃〜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
。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.
一方、本発明の方法２によって、■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）ｓ ） （Ｎｂ（
ＳｚＣｚ）Ｉ４）：＋ ）や式〔Ｌｉ （ｔｈｆ）ｚ
〕（Ｔａ（ＳｚＣｚＨａ）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ェニルホスホニウムと反応させ
れば目的とする■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
ェニルホスホニウムを反応させるにあたっては、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、通常は一４０℃〜５０℃、好ましくはθ℃〜２０℃
の範囲に設定すればよい。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.
上述の方法ｌあるいは方法２によれば、一般式（１）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ＣＤ
ＭＰ）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 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.
本発明の方法１，２によれば、高い収率でしかも高純度
の■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
反応によって、ニオブカルコゲニドやタンクルカルコゲ
ニドのｖ 族金ｉ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 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.
したがって、本発明の■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 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.
実施例１ にオブエタンジチオラート錯体の製造）五塩
化ニオブ（ＮｂＣ１ｓ） ６．８ ｇ （２５ミリモル
）をアセトニトリル５０ＩＩＩｌｔ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〔ＬｉＳ ＣＨｔＣＨａｓ Ｌｔ） ８．２ ｇ（
７７ミリモル）をアセトニトリル８０ｍ１ｔに懸濁した
懸濁液を、０℃水浴中で攪拌し、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
溶液となったが、そのまま１時間攪拌した。次に、デカ
ンテーションと濾過によっ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 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.
その後、得られた溶液に、臭化テトラフェニルホスホニ
ウム（（ＣａＨｓ）ｎＰ Ｂｒ） ９．６ ｇ （２３
ミリモル）をアセトニトリル４０ｍｌ１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。−晩、冷蔵庫に静置した後、粗結晶を濾取した。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.
粗結晶の収量は１３．６ ｇであり、収率は７７％であ
った。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）４０ｖａｌに溶解゛させて濾過し
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。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.
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ったり
元素分析値（％）
炭素 水素 窒素 硫黄
計算値 ５０．６８ ５．０４ １．７９ ２４．６
０実測値 ５０．６１ ４．９５ １．８４ ２４．
７５（（Ｃ，Ｈｓ）４Ｐ）（Ｎｂ（ＳｇＣｇＨｎ）Ｊ）
・ＤＭＦ。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.
組成式： ＮｂＣ−ａｚＨｓｑＮ ＯＰ Ｓ ｈ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
）。Composition formula: NbC-azHsqN OP Sh proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d6
).
６３．６６ （ＳＣＨｚ １２Ｈ，ｓ） 。63.66 (SCHz 12H, s).
７．８４ （（Ｃｉ、Ｈｓ）ａＰ ２０Ｈ，ｍ） 。7.84 ((Ci, Hs) aP 20H, m).
２．８２（ＤＭＦ Ｃ旦３ ６Ｈ，ａ）。2.82 (DMF Cdan 3 6H, a).
８．０４ （ＤＭＦ Ｉ Ｈ，５ｂｒ）遠赤外線吸収
スペクトル（Ｎｕｊｏｌ ＩＩＩｕｌｌ）４４０ｗ、
３５４ｍ、 ３３１ｎ （ａｍ−’）紫外−可視
光線吸収スペクトル（ＣＨｆｆＣＮ）λ、 ｎｍ （
１０−’ｔ、 Ｍ−’ｅｌｌ−’） ５２３ （０，４
８）３８６ （１，０２）、３２５ （１，１４）実施
例２にオブエタンジチオラーＨｆ体の製造）五塩化ニオ
ブ（ＮｂＣ１ｓ） ６．２ ｇ （２３ミリモル）をベ
ンゼン１００１１１に懸濁させ、０℃の水浴中で攪拌し
ながら、これにエタンジチオールのリチウム塩〔ＬｉＳ
ＣＨｚＣＨｉｓ Ｌｉ） ７．５ ｇ （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、残った赤褐色の固体にテトラヒドロフラン（ＴＨ
Ｆ）を注ぐと約１０分で赤色の溶液になった。これを濾
過しｔｌＡ縮したところ赤色結晶が得られた。収量は５
．９ｇ、収率は４３％（ＮｂＣ１ｓ基準）であった。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）ｓ ）（Ｎｂ（ＳｇＣｇＨｎ）＋
）で表わされるリチウム含有錯体であることがわか′
った。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.
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３５ａｌｌに溶かし、・これに臭
化テトラフェニルホスホニウム１．７６ｇ（４，２ミリ
モル）のアセトニトリル３０ｎ＋１溶液を添加した。そ
の結果、結晶が生成し、収量２．７ｇ、収率的９０％で
あった。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%.
この結晶を上記参考例１と同様の分析を行なったところ
、式（（Ｃ４Ｈ６）４Ｐ）（Ｎｂ（ＳｇＣｇＨｎ）コ〕
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, it was found that it had the formula ((C4H6)4P)(Nb(SgCgHn))
It was confirmed that it is a niobium ethanedithiolate complex represented by
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（ＴａＣ１ｇ） ４．０ ｇ （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って結
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った。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.
元素分析値（％）
炭素 水素 窒素 硫黄
計算値 ４５．５５ ４，５３ １．６１ ２２．１
１実測値 ４５．３１ ４．４９ １．６４ ２２．
００（（Ｃ６Ｈ３）ＪＰ）（Ｔａ（ＳｇＣｇＨｎ）ｚ
） ・ＤＭＦ。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.
組成式：ＴａＣ３ｓＨ＊＊Ｎ０ＰＳ６
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）。Compositional formula: TaC3sH**N0PS6 Proton nuclear magnetic resonance spectrum (dimethyl sulfoxide-d6).
δ３．８７ （ＳＣ−Ｌｌ ２）（、ｓ） 、 ’
７．８５ （（Ｃ＆且５）４Ｐ ２０ Ｈ，ｍ） 。δ3.87 (SC-Ll 2)(,s),'
7.85 ((C & 5) 4P 20 H, m).
２．８２（ＤＭＦ Ｃ且３ ６Ｈ，ｄ）。2.82 (DMF C and 3 6H, d).
８．０５ （ＤＭＦ Ｉ Ｈ，５ｂｒ）遠赤外線吸収
スペクトル（Ｎｕｊｏｌ ｍａｌｌ）４４２ｗ、
３３３ｍ、 ３０７ｍ （ｃｍ−’）紫外−可視光線
吸収スペクトル（ＣＨ３ＣＮ）λ、 ｎｍ （１０”
’ａ、 Ｍ−’ｃｆｆｉ−’） ４４１ （０，６２）
。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)
）＿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。(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.
はタンタルを示し、Ｘ＾１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ＬｉＳＣＨ＿２ＣＨ＿２ＳＬｉ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（Ｃ＿６Ｈ＿５）＿
４ＰＸ＾２（式中、Ｘ＾２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ェ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〔（Ｃ＿６Ｈ＿５）＿４Ｐ〕〔Ｍ（Ｓ＿２Ｃ＿２Ｈ
＿４）＿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。(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.
タンタルを示し、Ｘ＾１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ＬｉＳＣＨ＿２ＣＨ＿２ＳＬｉ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（Ｓ＿２Ｃ＿２Ｈ＿４）＿
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（Ｃ＿６Ｈ＿５）＿
４ＰＸ＾２（式中、Ｘ＾２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ェ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 〔（Ｃ＿６Ｈ＿５）＿４Ｐ〕〔Ｍ（Ｓ＿２Ｃ＿２Ｈ＿４
）＿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) 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.
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 true JPS6284093A (en) | 1987-04-17 |
| JPH0451557B2 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 |
|---|---|
| JPH0451557B2 (en) | 1992-08-19 |
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