Creation and Function of New Election-dificient Transition Metal Chalcogenide Complexs

新型缺电子过渡金属硫属化物配合物的制备和功能

• 批准号: 07404053
• 负责人: TATSUMI Kazuyuki
• 金额: $ 3.39万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07404053/
• 关键词: Molybdenu; Tungsten; Tantalum; Iron; Copper; Sulfide; Cluster; C-S Bond Cleavag; 銅; スルフィド錯体; セレンド錯体; チオラート錯体; ペンタメチルシクロペンタジェニル

We herewith summarize the results obtained under this research project.(1) A new lanthanide chemistry has been developed based on "hard" - "soft" interactions between lanthanide metals and S-donor ligands. We have isolated and structurally characterized [Li(thf)_2]_3[Yb_5S_3(S^tBu)_<12>] and [Li(tmeda)]-[YbCl_3(STsi)(tmeda)].(2) A series of Ta/Fe chalcogenide clusters have been synthesized, which have a common pentamethyl-cyclopentadienyl tantalum fragment. The reactions of "Cp^<**>Ta(S)_3Li_2" with iron chlorides produced (Et_4N)_2 [(Cp^<**>TaS_3)_2Fe] and Ta_2Fe_4E_9 (E=S,Se), the latter of which has a cluster framework closely related to the FeMo-Co structure.(3) The reactions of Cp^<**>TaCl (S^tBu) with hydrazines gave rise to Cp^<**>TaS (S^tBu) (eta^2-NMeNMeH) and Cp^<**>TaS (S^tBu) (eta^1-NNMe_2^tBu). Interestingly the latter complex contains a very rare amine-imide ligand.(4) We have carried out low temperature (100^4) solid state syntheses, in order to obtain new heterometallic sulfide clusters. For example, the reaction of [NH_4]_2 [MS_4] (M=Mo, W) with 2 equiv of [Cu(CH_3CN)_4] [PF_6] under the presence of 4 equiv of dppn (=Ph_2PCH_2PPh_2) in solid lead to the formation of [Cu_4(dppm)_4MS_4] [PF_6]_2 (M=Mo, W).(5) We have synthesized a series of W/Cu clusters with high nuclearity from the reactions between (PPh_4) - [Cp^<**>W(S)_3] and Cu(I) complexes. Examples are tetra-and octa-nuclear clusters [Cp^<**>WS_3Cu_3-Br_3]_2 and (Cp^<**>WS_3)_4Cu_4, and a 1-dimensional polymer [(Cp^<**>WS_3Ag_2)_2(mu-Br)_2]_n etc.(6) The reaction of FeCl_3 was found to promote C-S bond cleavage of [Cp^<**> Mo(StBu)_3 giving rise to a cubane cluster Cp^<**>_2Mo_2FeS_4Cl_2, which was then reacted with Li_2S_2 to generate an unusual tris-cubane cluster Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4).

我们在此总结了本研究项目所取得的成果。(1)基于镧系金属与S-给体配体之间的“硬”-“软”相互作用，发展了一种新的镧系化学。本文报道了[Li（thf）_2]_3[Yb_5S_3（S^tBu）_<12>]和[Li（tmeda）]-[YbCl_3（STsi）（tmeda）]的晶体结构。(2)合成了一系列Ta/Fe硫族化合物簇合物，它们都含有一个共同的五甲基钽碎片。“Cp^**&gt;Ta（S）_3Li_2”与铁的氯化物反应生成（Et_4N）_2 [（Cp^**&gt;TaS_3）_2Fe]和Ta_2Fe_4E_9（E=S，Se），后者具有与FeMo-Co结构密切相关的团簇骨架。(3)Cp^**&gt;TaCl（S^tBu）与肼反应生成Cp^**&gt;TaS（S^tBu）（eta^2-NNMe_2^tBu）和Cp^**&gt;TaS（S^tBu）（eta^1-NNMe_2^tBu）。有趣的是，后一种配合物含有非常罕见的胺-酰亚胺配体。(4)为了获得新的异金属硫化物簇合物，我们进行了低温（100^4）固相合成。例如，[NH_4]_2 [MS_4]（M=Mo，W）与2当量的[Cu（CH_3CN）_4] [PF_6]在4当量的dppn（=Ph_2PCH_2PPh_2）存在下反应，生成[Cu_4（dppm）_4MS_4] [PF_6]_2（M=Mo，W）。(5)通过（PPh_4）- [Cp^**&gt;W（S）_3]与Cu（I）配合物的反应，合成了一系列高成核度的W/Cu原子簇。例如四核和八核簇合物[Cp^** WS_3Cu_3-Br_3]_2和（Cp^** WS_3）_4Cu_4，以及一维聚合物[（Cp^** WS_3Ag_2）_2（mu-Br）_2]_n等。(6)发现FeCl_3促进[Cp^**&gt; Mo（StBu）_3的C-S键断裂，生成立方烷团簇Cp^**&gt;_2Mo_2FeS_4Cl_2，然后与Li_2S_2反应生成不寻常的三立方烷团簇Cp^**&gt;_2Mo_2Fe_2S_4]_3（mu-S_4）。

项目成果

H.Kawaguchi: "Construction of a Cyclic Tricubane Cluster [Cp^*_2Mo_2Fe_2S_4]_3(mu-S_4)_3 from the Mo_2Fe_2S Single Cubane Component." J.Am.Chem.Soc.119・44. 10871-10872 (1997)

H. Kawaguchi：“从 Mo_2Fe_2S 单立方烷组分构建环状三立方烷簇 [Cp^*_2Mo_2Fe_2S_4]_3(mu-S_4)_3”。J.Am.Chem.Soc.119・44 (1997)。

H.Kawaguchi, K.Yamada, S.Ohnishi, and K.Tatsumi: "Construction of a Cyclic Tricubane Cluster [Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4)_3 from the Mo_2Fe_2S_4 Single Cubane Component." J.Am.Chem.Soc.119. 10871-10872 (1997)

H.Kawaguchi、K.Yamada、S.Ohnishi 和 K.Tatsumi：“从 Mo_2Fe_2S_4 单立方烷组分构建环状三立方烷簇 [Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4)_3”。

K.Tatsumi: "Synthesis of Organometallic Compounds:A Practical Guide" Wiley, 44 (1997)

K.Tatsumi：“有机金属化合物的合成：实用指南”Wiley，44 (1997)

H.Kawaguchi, and K.Tatsumi: "A Facile Route to the Trithiotungsten (VI) Complex (PPh_4) [(C_5Me_5)-W(S)_3] via C-S Bond Cleavage of Ethanedithiolate and Its Reactions with Alkyl Halides and Alkynes" J.Am.Chem.Soc.117. 3885-3886 (1995)

H.Kawaguchi 和 K.Tatsumi：“通过乙烷二硫醇的 C-S 键断裂及其与烷基卤化物和炔烃的反应，获得三硫钨 (VI) 络合物 (PPh_4) [(C_5Me_5)-W(S)_3] 的简便途径” J

H.Kawaguchi and K.Tatsumi: "Synthesis of (Pentamethylcyclopentadienyl) tantalum Sulfido Complexes via C-S Bond Cleavage of Triphenylmethanethiolate and Formation of a Novel Trithioborato Ligand." Organometallics. 16. 307-309 (1997)

H.Kawaguchi 和 K.Tatsumi：“通过三苯基甲硫醇的 C-S 键断裂合成（五甲基环戊二烯基）钽硫络合物并形成新型三硫代硼酸配体。”