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)二聚体及其相关化合物的核磁共振。测定了Senen Ru(III)多核配合物的核磁共振波谱，这些配合物本质上是通过Ru(III)-Ru(III)相互作用而具有抗磁性的。研究了氧化态、施主原子和金属-金属键对化学位移的影响。羧酸桥联多核配合物的合成与表征。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)具有CH2COO^&lt；2-Gt；(2)在吡嗪桥联的氧、羧基桥联的Ru三核簇合物中，我们成功地在三核单元之间产生了“混合价”状态。(3)我们发现大的(20-26)元Curtis大环(完全饱和形式)通过附加两个小的桥联配体如OR^-、OH^-或CH_3COO^-来作为铜(II)的双核配体。这类铜(II)二聚体一般表现出反铁磁相互作用。相互作用的程度对二聚体的核心结构非常敏感。(4)在氧代、羧基桥联的三核Ru与CO末端的配体中，发现了一种新的光诱导配体取代。含三核Ru簇合物的大分子配合物的合成。合成了6个新的由4-聚乙烯基吡啶与氧、羧基桥联的Ru三核簇合物组成的大分子配合物。在一定条件下，涂覆在玻碳电极上的络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.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

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+>。"

S. Ikari, Y. Sasaki, A. Nagasawa, C. Kabuto, and T. Ito: ""A New Mixed Molybdenum-Tungsten Dimer Complex, Bis(mu-oxo)(mu-oxo)(mu-ethylenediaminetetraacetato-N, N')oxomolybdenum(V)-oxotungstate(V)"" Inorg. Chem.28. 1248 (1989)

S. Ikari、Y. Sasaki、A. Nagasawa、C. Kabuto 和 T. Ito：“一种新型混合钼钨二聚体复合物，双(mu-oxo)(mu-oxo)(mu-乙二胺四乙酸-N，