Syntheses, Structures, and Characterization of Sulfur-Bridged Mixed-Metal Cluster Complexes

硫桥混合金属簇合物的合成、结构和表征

• 批准号: 02453043
• 负责人: SHIBAHARA Takashi
• 金额: $ 3.26万
• 依托单位: Okayama University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453043/
• 关键词: Sulfur-Bridge; Cubane; Cluster; Mixed-Metal; Molecular Mrbital; Exchange; キュバン型; DVーVα

Mixed-metal cluster compounds have been studies extensively. Above all, mucti interest has been focused on(incomplete)cubane-type clusters. We have reported the reaction of the incomplete cubane-type aqua ion [Mo_3S_4(H_2O)_9]^<4+> with metals(Fe, Co, Ni, Cu, Sn, and lig)or metal ion(Sn^<2+>) to give mixed metal cubane-type aqua cluster ions with Mo_3MS_4 cores. Three kinds of cubanetype mixed metal cores have been reported so far : single, double, and sandwich.The following are main results obtained.1. A new type of replacement reactions has been found.Mo_3MS_4^<4+> (ap) + Cu_<2+> -> Mo_3CuS_4^<4+> (aq) + M^<2+> (M = Fe, Ni)2. Molecular orbital calculations have been done on incomplete cubane-type sulfide- or oxo-bridged molybdenum cluster compounds [Mo_3S_4(H_2O)_9]^<4+> and [Mo_3O_4(H_2O)_9]^<4+> using DV-Xalpha method, where Slater transition method was applied to get better results.3. Facile synthetic methods for [Mo_3S_4(H_2O)_9]^<4+> and [W_3S_4(H_2O)_9]^<4+> have been developed using (NH_4)_2MoS_4 and (NH_4)_2WS_4, respectively.4. Mixed metal clusters[(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9]^<8+>, [Mo_3InS_4(pts)_2-(H_2O)_<10>]^<3+>, and [Mo_2WNiS_4(H_2O)_<10>]^<4+> have been newly synthesized and the structures determined by X-ray crystallography. Electrochemical analyses of these compounds have also been done.

混合金属簇化合物已被广泛研究。最重要的是，人们的兴趣主要集中在（不完整的）立方烷型簇上。我们报道了不完全立方烷型水离子[Mo_3S_4(H_2O)_9]^<4+>与金属(Fe、Co、Ni、Cu、Sn和lig)或金属离子(Sn^<2+>)的反应，得到以Mo_3MS_4为核的混合金属立方烷型水簇离子。目前已报道三种立方型混合金属磁芯：单层、双层和夹层。主要研究结果如下： 1．发现了一种新型置换反应：Mo_3MS_4^<4+> (ap) + Cu_<2+> -> Mo_3CuS_4^<4+> (aq) + M^<2+> (M = Fe, Ni)2。采用DV-Xalpha方法对不完全立方烷型硫桥或氧桥钼簇化合物[Mo_3S_4(H_2O)_9]^<4+>和[Mo_3O_4(H_2O)_9]^<4+>进行了分子轨道计算，并采用Slater过渡法得到了较好的结果。 3．分别使用(NH_4)_2MoS_4和(NH_4)_2WS_4开发了[Mo_3S_4(H_2O)_9]^<4+>和[W_3S_4(H_2O)_9]^<4+>的简便合成方法。4．新合成了混合金属簇[(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9]^<8+>、[Mo_3InS_4(pts)_2-(H_2O)_<10>]^<3+>和[Mo_2WNiS_4(H_2O)_<10>]^<4+>， 通过X射线晶体学测定结构。还对这些化合物进行了电化学分析。

项目成果

Takashi Shibahara: "Syntheses and Electrochemistry of Incomplete Cubane-Type Clusterswith M_3S_4 Cores (M=Mo,W).X-Ray Structures of 〔W_3S_4(H_2O)_9〕(CH_3・C_6H_4・-SO_3)_4・9H_2O),Na_2〔W_3S_4(Hnta)_3〕・5H_2,and (bpyh)_5〔W_3S_4(NCS)_9〕・3H_2O" Inorganic Chemist

Takashi Shibahara：“不完全古巴烷的合成和电化学-这些具有M_3S_4核心的簇（M=Mo,W）。W_3S_4（Hnta）_3〕·5H_2，和（bpyh）_5〔W_3S_4（NCS）_9）·3H_2O”无机化学家

Takashi Shibahara: "SulfurーBridged Incomplete Cubaneーtype Mixed Metal Cluster Compounds of Molybdenum(IV) and Tungsten(IV).Syntheses,Characterization,and…" Inorganic Chemistry.

Takashi Shibahara：“钼（IV）和钨（IV）的硫桥不完全古巴烷型混合金属簇化合物。合成、表征和……”无机化学。

Hiromi Aikoh: "A New Method for the Determination of Mercury by Spectrophotometry Using Incomplete Cubane-Type Molybdenum Aqua Ion,Mo_3S_4(aq)^<4+>" Physiol.Chem.Phys. & Med.NMR. 22. 187-192 (1990)

Hiromi Aikoh：“使用不完全古巴烷型钼水离子，Mo_3S_4(aq)^<4 > 分光光度法测定汞的新方法”Physiol.Chem.Phys。

Takashi Shibahara: "Reaction of 〔Mo_3S_4(H_2O)_9〕^<4+> with Cobalt and Mercury.Syntheses and X-Ray Structures of Double Cubane-Type Cluster,〔(H_2O)_9Mo_3S_4CoCoS_4Mo_3-(H_2O)_9〕(CH_3・C_6H_4・SO_3)・18H_2O and Sandwich Cubane-Type Cluster,〔(H_2O)_9-" Chemist

柴原隆：“〔Mo_3S_4(H_2O)_9〕^<4+>与钴和汞的反应。双古巴烷型团簇的合成和X射线结构，〔(H_2O)_9Mo_3S_4CoCoS_4Mo_3-(H_2O)_9〕(CH_3・C_6H_4・SO_3)・18H_2O和夹心古巴烷型团簇，〔(H_2O)_9-"化学家

Takashi Shibahara: "Cubane-Type Mixed Metal Clusters With Mo_3NiS_4 Cores.Syntheses,Charactrization,and X-Ray Structures of 〔Mo_3NiS_4(H_2O)_<10>〕(CH_3・C_6H_4・-SO_3)4・7H_2O and Ca_<2.5>〔Mo_3NiS_4(Hnta)(nta)_2Cl〕・14H_2O" Inorganic Chemistry. 30. 2693-2699

Takashi Shibahara：“具有 Mo_3NiS_4 核的立方烷型混合金属团簇。[Mo_3NiS_4(H_2O)_<10>](CH_3・C_6H_4・-SO_3)4・7H_2O 和 Ca_<2.5> 的合成、表征和 X 射线结构[Mo_3NiS_4(Hnta)(nta)_2Cl]・14H_2O" 无机化学. 30. 2693-2699