Chemical Consequences of Assemblage of Transition Metal Ions or Metal Complexes

过渡金属离子或金属络合物聚集的化学后果

• 批准号: 01430009
• 负责人: ITO Tasuku
• 金额: $ 11.84万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01430009/
• 关键词: Polynuclear Metal Complex; Metal Cluster Complex; ^<99>Ru NMR; Carboxylate Bridged Complex; Macromolecular Complex; Redox Behavior; ^<99>Ru NMR; 金属核; ニオブ-93ーNMR; 位置選択的反応性; 多彩な酸化還元挙動

1. ^<99>Ru NMR of Ru (III) Dimer and Related Compounds. ^<99>Ru NMR spectra have been measured on senen Ru (III) polynuclear complexes, which are essentially diamagnetic through Ru (III)-Ru (III) interaction. Effects of oxidation sate, donor atom, and metal-metal bond upon chemical shift have been studied.2. Synthesis and Characterization of Carboxylate Bridged Polynuclear Complexes. More than 20 new compounds have been synthesized, and their properties have been studied from the view point of the assemblage effects.(1) Novel Pt (III) dimers in which CH_2COO^<2-> bridges two Pt's through C and O have been synthesized.(2) In a pyrazine bridged dimer of the oxo, carboxylato bridged Ru trinuclear cluster, we produced successfully "mixed valence" states between the trinuclear units.(3) We found that large (20-26) membered Curtis macrocycles (fully saturated form) act as a dinucleating ligand for Cu (II) by taking up two additional small bridging ligands such as OR^-, OH^-, or CH_3COO^-. Such Cu (II) dimers show generally anti-ferromagnetic interaction. The degree of the interaction was found to be very sensitive to the core structure of the dimer.(4) A new photo-induced ligand substitution was found in oxo, carboxylato bridged trinuclear Ru complexes with the CO terminal ligand.3. Synthesis of Macromolecular Complexes having Trinuclear Ru Cluster Unit. Six new macromolecular complexes comprised of 4-polyvinylpyridine and oxo, carboxylato bridged Ru trinuclear cluster have been synthesized. Under certain conditions, thin film of the complex coated on a glassy carbon electrode showed reversible redox response in an aqueous solution.

1.Ru(III)二聚体和相关化合物的1 99 Ru NMR。已在senen Ru(III)多核配合物上测量了99 Ru NMR谱，该多核配合物基本上通过Ru(III)-Ru(III)相互作用而具有抗磁性。研究了氧化态、给体原子、金属-金属键对化学位移的影响。 2．羧酸桥多核配合物的合成和表征。已合成了20多个新化合物，并从组装效应的角度研究了它们的性质。(1)新型Pt(III)二聚体，其中CH_2COO^<2->通过C和O桥接两个Pt。 (2)在氧代、羧基桥接Ru三核簇的吡嗪桥二聚体中，我们成功地产生了三核之间的“混合价”态(3) 我们发现大 (20-26) 元柯蒂斯大环化合物（完全饱和形式）通过吸收两个额外的小桥连配体（例如 OR^-、OH^-）作为 Cu (II) 的双核配体，或 CH_3COO^-。此类 Cu (II) 二聚体通常表现出反铁磁相互作用。研究发现相互作用的程度对二聚体的核心结构非常敏感。(4)在CO端配体的氧代、羧基桥接的三核Ru配合物中发现了一种新的光诱导配体取代。3．具有三核Ru簇单元的大分子配合物的合成。合成了六种由4-聚乙烯吡啶和氧代、羧基桥接Ru三核簇组成的新大分子配合物。在一定条件下，涂覆在玻碳电极上的配合物薄膜在水溶液中表现出可逆的氧化还原反应。

项目成果

S.Ikari: "Asymmetric Distortion of bis(muーoxo)bis(oxotungstate(V))Complexes.Crystal Structure of Bis(muーoxo)(muーN,N'ー(R)ーpropylenediaminetetaacetato)bis(oxotungstate(V))" Inorganic Chemistry. 29. 53-56 (1990)

S.Ikari：“双（muーoxo）双（oxotungstate（V））配合物的不对称变形。双（muーoxo）（muーN，Nー（R）ー丙二胺四乙酸）双（oxotungstate（）的晶体结构（ V))”无机化学。29. 53-56 (1990)

K.Nakata,A.Nagasawa,N.Soyama,Y.Sasaki,and T.Ito: "Kinetic Studies on the Terminal Ligand Substitution Reactions of AcetateーBridged Trinuclear Molybdenum and Tungsten Cluster Complexes [Mo_3(CCH_3)(O)(CH_3COO)_6(L)]^+ and [W_3(O)(CH_3COO)_6(H_2O)_3]^<2+>."

K.Nakata、A.Nagasawa、N.Soyama、Y.Sasaki 和 T.Ito：“乙酸桥三核钼和钨簇配合物末端配体取代反应的动力学研究 [Mo_3(CCH_3)(O)(CH_3COO) )_6(L)]^+ 和 [W_3(O)(CH_3COO)_6(H_2O)_3]^<2+>。"

K.Nakada,A.Nagasawa,Y.SaSaki,and T.Ito: "Redox Properties of a Series of Iron(III) Trinuclear Carboxylates,[Fe_3(μーO)(μーRCO_2)_6(L)_3]^<n+>" Chemistry Letters. 753-756 (1989)

K. Nakada、A. Nagasawa、Y. SaSaki 和 T. Ito：“一系列三核羧酸铁 (III) 的氧化还原性质，[Fe_3(μーO)(μーRCO_2)_6(L)_3]^ <n+>”化学快报。753-756 (1989)

T.Yamaguchi,Y.Sasaki,and T.Ito: "Unusual C,OーBridging Coordination of Acetate and Acetylacetonate Ligands in the Platinum Clusters,[Pt^<III>_2(CH_2COO)_2(CH_3COO)_2Cl_2]^<2-> and Pt^<II>_4(CH_3COO)_4(CH_3COCHCOCHCC3DD)_4." Journal of American Chemical Soc

T. Yamaguchi、Y. Sasaki 和 T. Ito：“铂簇中乙酸盐和乙酰丙酮酸配体的不寻常 C,O 桥接配位，[Pt^<III>_2(CH_2COO)_2(CH_3COO)_2Cl_2]^<2 -> 和 Pt^<II>_4(CH_3COO)_4(CH_3COCHCOCHCC3DD)_4。”美国化学会杂志

T.Yamaguchi: "Unusual C,OーBridging Coordination of Acetate and Acetylacetonate Ligands in the Platinum Clusters,[Pt^<III>_2(muーCH_2COOーC,O)_2(muーCH_3COOーO,O')_2Cl_2]^<2-> and Pt^<II>_4(muーCH_3COOーO,O')_4(muーCH_3COCHCOCH_3ーO,C^3)_4." Journal of The America

T.Yamaguchi：“铂簇中乙酸盐和乙酰丙酮酸配体不寻常的 C,Oー桥配位，[Pt^<III>_2(muーCH_2COOーC,O)_2(muーCH_3COOーO,O)_2Cl_2 ]^<2-> 和 Pt^<II>_4(muーCH_3COOーO,O)_4(muーCH_3COCHCOCH_3ーO,C^3)_4。”《美国杂志》