Second Generation Octahedral Coordination Chemistry based on Hexametal Cluster Units

基于六金属团簇单元的第二代八面体配位化学

• 批准号: 15350029
• 负责人: SASAKI Yoichi
• 金额: $ 9.86万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350029/
• 关键词: Metal Cluster Complexes; Hexanuclear Metal Complexes; Rhenium Complexes; Emissive Complexes; Ligand Substitution Reactions; Self-assembled Monolayers; Redox Reactions; Ligand-Ligand Interactions

Octahedal hexametal clusters are known for various transition metal ions. Among them, those with d^4 metal ions such as Re(III), Mo(II) and W(II) are particularly stable with twelve electron-precise metal-metal single bonds. In this project, d^4 octahedral hexanuclear cluster complexes are considered as a target of a second generation of octahedral metal coordination chemistry. The purpose of this study is to clarify the similarity and difference between the octahedral cluster complexes and simple mononuclear octahedral complexes. The results are summarized as follows. (i) Ligand substitution properties. Kinetic study of the ligand substitution reactions at the terminal sites of the hexarhenium(III) clusters revealed that pyridine ligand is more rapidly substituted than chloride. This is in reverse trend from that of mononuclear complexes where less basic chloride ligand is replaced more easily. (ii) Redox reactions. Hexarhenium(III) complexes undergo one-electron oxidation. The redox … More potential shifts to positive direction as the number of terminal pyridine ligands increases in the mixed terminal pyridine-chloride system. This is in reverse direction from the expectation by considering the ligand basicity. The two facts, (i) and (ii), manifest unique characteristics of the hexametal clusters ; good π accepting and poor π donoating properties as opposed to typical low-spin d^6 mononuclear metal centers. (iii) Emissions. The d^4 octahedral clusters exhibit strong red emissions. Detailed temperature dependence of the emissions revealed curious behavior of emission life-times and emission energies. These results were successfully analyzed by considering four excited state sublevels. (iv) Self-assembled monolayers. Hexarhenium clusters were successfully fixed onto the gold electrode surfaces by using strong Au-S bond. The S-site was introduced to the ligand pyridine derivatives attached to the hexanuclear unit. Also the hexarhenium cluster unit was chemically combined to oxo-centered triruthenium unit both in solution and on the gold surface. The surface electrochemistry of the hexarhenium clusters and triruthenium-hexarhenium hybrid complexes have been studied. These results (i) - (iv) revealed important differences and similarities of the octahedral hexametal cluster complexes and simple mononuclear metal centers. Less

八面体六金属团簇是已知的各种过渡金属离子。其中，含Re(III)、Mo(II)和W(II)等d^4金属离子的化合物特别稳定，具有12个电子精确的金属-金属单键。在这个项目中，d^4个八面体六核簇合物被认为是第二代八面体金属配位化学的目标。本研究的目的是阐明八面体簇合物与简单单核八面体配合物的异同。研究结果总结如下。(I)配体取代性质。对六茂金属簇末端配体取代反应的动力学研究表明，吡啶配体的取代速度比氯化物更快。这与单核络合物的趋势相反，在单核络合物中，碱性较低的氯化物配体更容易被取代。(Ii)氧化还原反应。六价锗(III)络合物发生单电子氧化。氧化还原…在混合末端吡啶-氯化体系中，随着末端吡啶配体数目的增加，更多的电势向正方向移动。考虑到配体的碱性，这与预期的方向相反。(I)和(Ii)这两个事实表明了六金属团簇的独特特征：与典型的低自旋d^6单核金属中心相比，具有良好的π接受性和较差的π捐献性能。(Iii)排放。D^4八面体团簇表现出很强的红光发射。发射的详细温度依赖关系揭示了发射寿命和发射能量的奇怪行为。通过考虑四个激发态子能级，成功地分析了这些结果。(4)自组装单分子膜。利用较强的Au-S键，成功地将六茂铁团簇固定在金电极表面。S位被引入到连接在六核单元上的配体吡啶衍生物中。另外，在溶液中和金表面上，六茂基团簇单元都被化学结合成氧中心的三Ru单元。研究了六价金属簇合物和三Ru-六价金属杂化络合物的表面电化学行为。这些结果(I)-(IV)揭示了八面体六金属簇合物和单单核金属中心的重要区别和相似之处。较少

项目成果

A Pair of Seven-Coordinate Oxorhenium Complexes: [ReIVO(tpen)]2+ and [ReVO(tpen)]3+ (tpen = N,N,N′,N′-Tetrakis(2-pyridylmethyl)ethylenediamine)

一对七配位氧铼配合物：[ReIVO(tpen)]2+ 和 [ReVO(tpen)]3+ (tpen = N,N,N′,N′-四(2-吡啶基甲基)乙二胺)

• DOI: 10.1246/bcsj.77.1139
• 发表时间: 2004
• 期刊: Bulletin of the Chemical Society of Japan
• 影响因子: 4
• 作者: Haichao Jin;S. Ikari;Kimiko Kobayashi;K. Umakoshi;H. Sugimoto;Ayako Mitani;M. Abe;Y. Sasaki;Tasuku Ito
• 通讯作者: Tasuku Ito

Switching of the Electronic Communication between Two {Ru(trpy)(bpy)} (trpy = 2,2' : 6',2"-Terpyridine and bpy = 4,4'-Bipyridine) Centers by Protonation on the Bridging Dimercaptothiadiazolato Ligand

通过桥接二巯基噻二唑配体上的质子化在两个 {Ru(trpy)(bpy)}（trpy = 2,2 : 6,2"-三联吡啶和 bpy = 4,4-联吡啶）中心之间进行电子通信的切换

• 发表时间: 2005
• 期刊: Inorganic Chemistry 44巻15号
• 作者: K.Omata;N.Hoshi;K.Kabuto;C.Kabuto;Y Sasaki;M.Abe;K.Uruma;Y.Tajika;H.Tannai
• 通讯作者: H.Tannai

X-ray Structure and Electrochmical Properties of a Tpen-Bridged Hetero-Binuclear Complex fac-, fac-[Re^<VII>O_3(μ-tpen)Re^I(CO)_3](PF_6)_2 where Tpen is N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine

Tpen桥异双核配合物fac-, fac-[Re^<VII>O_3(μ-tpen)Re^I(CO)_3](PF_6)_2的X射线结构和电化学性质，其中Tpen为N， N,N,N-四(2-吡啶甲基)乙二胺

• 发表时间: 2005
• 期刊: Journal of Nuclear and Radiochemical Science 6巻3号
• 作者: K.Omata;N.Hoshi;K.Kabuto;C.Kabuto;Y Sasaki;M.Abe;K.Uruma;Y.Tajika;H.Tannai;W.Zhou;N.Kitamura;E.Sakuda;H.Araki;Y.Sasaki;T.Tabeya
• 通讯作者: T.Tabeya

Preparation, Structures, and Redox and Emission Characteristics of Isothio-cyanate Complexes of Hexarhenium(III) Clusters, [Re_6(μ_3-E)_8(NCS)_6]^<4->.

六铼(III)簇异硫氰酸酯配合物的制备、结构、氧化还原和发射特性，[Re_6(μ_3-E)_8(NCS)_6]^<4->。

• 发表时间: 2003
• 期刊: Inorganic Chemistry 42巻10号
• 作者: Y.Sasaki;M.Abe;Hai-Yin Jin;Shen Ye;Daisuke Akashi;Yoichi Sasaki;O.Asada;K.Fukushima;H.Tannai;A.Mitani;M.Suzuki;M.Abe;T.Yoshimura
• 通讯作者: T.Yoshimura

A.Mitani: "η^3-Coordination of Hexadentate N, N, N', N'-Tetrakis (2-pyridyl-methyl)ethylenediamine (tpen) to a Mononuclear fac-Re^<VII> Center"Chemistry Letters. 34巻6号. 502-503 (2003)

A.Mitani：“η^3-六齿 N、N、N、N-四（2-吡啶基甲基）乙二胺 (tpen) 与单核 fac-Re^<VII> 中心的配位”《化学快报》34。第 6 卷. 502-503 (2003)