Kinetic study of metal-metal bonded rhenium complexes

金属-金属键合铼配合物的动力学研究

• 批准号: 08044046
• 负责人: SASAKI Yoichi
• 金额: $ 6.08万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08044046/
• 关键词: rhenium Complexes; redox reactions; X-ray structural analysis; oxo-bridged complexes; metal-cluster complexes; kinetic studies; carboxylate-bridged complexes; metal-metal multiple bond; オキソ錯体; 金属間結合; 金属間相互作用; 複核錯体; ロジウム錯体

The purpose of this project is to understand the correlation between the oxidation states and reactivity and that of metal-to-metal interaction and redox properties by using rhenium complexes. Rhenium is the most versatile element with respect to its variety of oxidation states, and thus its complexes are the most appropriate to study redox preperties of metal complexes. Various important complexes have been prepared at Hokkaid Universty, and their reactivities have been studied by the foreign colleagues. Also, Dr.Sayse11 of the University of Newcastle-upon-Tyne and Dr.Botha of the University of Orange-Free-State, stayd at Hokkaido University for 3 months each and contributed to significant progress of the project.By using N,N,N,O-and N,N,O-type chelating ligands, we have isolated several mononuclear rhenium (V) complexes having incompletely chelated ligands. X-Ray structural determination of these complexes revealed complex formation steps of these chelating ligands, information which … More is impossible to obtain by using substitution labile metal ions. Dinuclear rhenium doubly oxo-bridged complexes have been isolated in two neighboring oxidation states, (III,IV) and (IV,IV). Their structural and redox studies show the correlation between the Re-Re bond-order and redox reactions. Study on hexanuclear rhenium sulfide clusters also revealed characteristic properties of Re-Re bond. The hexarhenium cluster, [Re_6S_8(H_2O)_6]_<2+> clusters, shows unexpectedly slow anation reactions with Cl^- or NCS^-. The remarkable inertness is difficult to understand for mononuclear rhenium (III) complexes and the effect of metal-metal bond should be taken into account. This inert nature enabled us to prepare partially substituted species of the type, [Re_6S_8(pyridine)_<6-n>Cl_n]^<(2-n)+>(n=1-3). Further studies to prepare the hexarhenium (III) complexes with pyridine derivative ligands show some redox interaction between the ligands at hexarhenium center.We have also studied redox reactions of some dinuclear ruthenium (III) complexes with oxide and acetate bridges. Protonation at the oxide bridge remarkable change the redox potentials of the diruthenium moiety. Relevance of the proton-coupled redox reactions to some enzyme dimetal active centers have been suggested. Less

本研究的目的是通过使用金属配合物来了解氧化态和反应性之间的相关性以及金属与金属相互作用和氧化还原性质之间的相关性。铼是最具多样性的氧化态元素，因此铼的配合物最适合研究金属配合物的氧化还原性质。福建大学合成了多种重要的配合物，国外同行对其反应性进行了研究。此外，纽卡斯尔大学的Sayse博士和奥兰治自由州大学的博塔博士也分别在北海道大学工作了3个月，为该项目的重大进展做出了贡献。X射线结构测定揭示了这些螯合配体的络合物形成步骤， ...更多信息 是不可能通过使用取代不稳定的金属离子获得的。双核双氧桥配合物已被分离出两个相邻的氧化态，（III，IV）和（IV，IV）。它们的结构和氧化还原研究表明Re-Re键序和氧化还原反应之间的相关性。对六核硫化铼簇合物的研究也揭示了Re-Re键的特征。六铼簇合物[Re_6S_8（H_2O）_6]_<2+>与Cl^-或NCS^-的反应出乎意料地慢。单核配合物的惰性是很难理解的，金属-金属键的影响应该考虑在内。这种惰性性质使我们能够制备部分取代的[Re_6S_8（吡啶）_<6-n>Cl_n]^&lt;（2-n）+&gt;（n=1-3）型化合物。进一步研究了吡啶衍生物配体与六铼（III）配合物的反应，发现六铼中心的配体之间存在氧化还原相互作用，我们还研究了一些具有氧化物桥和乙酸根桥的双核钌（III）配合物的氧化还原反应。氧化物桥上的质子化显著改变了二钌部分的氧化还原电位。质子偶联氧化还原反应与某些酶的双金属活性中心有关。少

项目成果

J. Mattheus Botha: "Chelation Processes to an Oxorhenium(V) Center by N,N,N,O-Tetradentate and N,N,O-Tridentate Ligands as Verified by structural and Mechanistic Studies." Inorganic Chemistry. No.7(印刷中). (1998)

J. Mattheus Botha：“N,N,N,O-四齿配体和 N,N,O-三齿配体对氧铼 (V) 中心的螯合过程已通过无机化学研究验证。” （出版中）。

Hideki Sugimoto, et al: "A Series of Oxorhenium (V) Complexes Containing Tridentate Tris (2-pyridylmethyl) amine Bearing One Free 2-Pyridylmethyl Arm" Chemistry Letters. No.6. 541-542 (1997)

Hideki Sugimoto 等人：“一系列含有带有一个自由 2-吡啶甲基臂的三齿三（2-吡啶甲基）胺的氧铼 (V) 配合物”化学快报。

Hideki Sugimoto, et al: "Oxorhenium (V) Complex of Amidophenolate : Structure and Redox Characteristics." Chemistry Letters. No.3. 197-198 (1998)

Hideki Sugimoto 等人：“氨基酚盐的氧铼 (V) 络合物：结构和氧化还原特性。”

Delanie Lamprecht: "Carbonyl(1,3-diphenyl-1,3-propanedionato-κ^2O,O]triphenylphosphinerhodium(I)." Acta Crystallographica,Section.C. C53(No.10). 1403-1405 (1997)

Delanie Lamprecht：“羰基(1,3-二苯基-1,3-丙二酮-κ^2O,O]三苯基膦铑(I)。”晶体学报，C. C53 节(No.10)。1403-1405 (1997)

Masaaki Abe: "Lewis Acid Trifluoroboran Coordination to trans-Dioxorhenium(V) Moiety: Structural and Spectroscopic Characterization of trans-[Re(O)(OBF_3)(1-Meim)_4](BF_4)." Chemistry Letters. No.10. 1073-1074 (1997)

Masaaki Abe：“刘易斯酸三氟硼烷与反式二氧铼(V)部分的配位：反式-[Re(O)(OBF_3)(1-Meim)_4](BF_4)的结构和光谱表征。”