Characteristic Reactivties and Functions of Metal Complexes containing Hypodentate Ligands.

含有次齿配体的金属配合物的特征反应性和功能。

• 批准号: 12440183
• 负责人: SASAKI Yoichi
• 金额: $ 8.96万
• 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: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440183/
• 关键词: Hypodentate Ligands; Transition Metal Coplexes; Photoluminescence; X-Ray Structural Analysis; Dynamic Exchange; Redox Reactions; Heavy Transition Elements; Platinum Complexes; レニウム錯体; ルテニウム錯体; 発光スペクトル; レニウムカルボニル錯体; オキソバナジウム錯体

Hypodentate ligand is defined as a ligand in which fewer than the maximum possible number of donor atoms are bonded to metal centers. The purpose of the study is to prepare various new complexes containing such ligands and to investigate their reactivities and functional characteristics. In particular we have paid special attention to luminecent complexes as the control of photophysical properties by using uncoordinated ligand moieties are promising. The results obtained by using polypyridyl ligands such as tris(2-pyridylmethyl)amine (tpa) and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) are as follows, (i) A series of planar Pt(II) and Pd(II) complexes with these ligands all have uncoordinated arms. The exchange of the free and coordinated arms have been found in the order Pt(II) < Pd(II) and tpa < tpen. (ii) Luminescent [Re(CO)_3(tpa)]^+ has been prepared which also has one uncoordinated arm that does not undergo exchange with the coordinated ones. (iii) V^<IV>O complexes of tpa has fully coordinated tpa (tetradentate), different from ReO-tpa complexes which have tridentate tpa, but with tpen V^<IV>O complex containing hypodentate ligand has been isolated. With the diphosphine ligands Ph_2P(CH_2)_nPPh_2 (n = 1 - 5), a series of luminescent hexarhenium cluster complexes containing monodentate diphosphines have been obtained. For the hexarhenium unit, we have also successfully introduced giant ligands free base pyridylporphyrines. We have also used a small polydentate ligand, 2.5-dimercapto-1,3,4-thiadiazole(McMTH). The complexes prepared include those containing a monodentate McMT are [Pt(terpy) (McMT)]^+ and [Ru(terpy)(bpy)(McMT)]^+. They react with another Pt(terpy)-unit to form homo and hetero dinuclear complexes. Furthermore various type of Cu(I) and Ag(I) complexes of McMT ligands have been obtained. All these McMT complexes are strongly luminescent.

亚配位基配体定义为其中少于最大可能数目的供体原子键合到金属中心的配体。本研究的目的是制备各种新的含此类配体的配合物，并研究它们的反应性和功能特性。特别是，我们已经特别注意到发光配合物的控制的物理性质，通过使用非配位的配体部分是有前途的。用三（2-吡啶基甲基）胺（tpa）和N，N，N ′，N ′-四（2-吡啶基甲基）乙二胺（tpen）等多吡啶基配体合成的铂（Ⅱ）和钯（Ⅱ）配合物均具有非配位臂。自由臂和配位臂的交换顺序为Pt（II）< Pd（II）和tpa < tpen。(ii)制备了一种发光化合物[Re（CO）_3（tpa）]^+，它也有一个不与配位臂发生交换的非配位臂。(iii)tpa的V^<IV>O配合物具有完全配位的tpa（四齿），不同于具有三齿tpa的ReO-tpa配合物，但与tpen的V^<IV>O配合物分离出含有次齿配体的配合物。以双膦配体Ph_2P（CH_2）_nPPh_2（n = 1 - 5）为配体，合成了一系列含单齿双膦的六铼原子簇发光配合物。对于六铼单元，我们还成功地引入了巨型配体游离碱吡啶基卟啉。我们还使用了一个小的多齿配体，2.5-二巯基-1，3，4-噻二唑（McMTH）。所制备的配合物包括含有单齿McMT的配合物[Pt（terpy）（McMT）]^+和[Ru（terpy）（bpy）（McMT）]^+。它们与另一个Pt（三联吡啶）单元反应形成同核和异核配合物。此外，还得到了各种类型的McMT配体的Cu（I）和Ag（I）配合物。所有这些McMT配合物都具有很强的发光性。

项目成果

Tetsuaki Fujihara, et al.: "Synthesis, Properties and Crystal Structure of a Novel Anthracen e-Bridged Mo-Zn Porphyrin Dimer"Inorganic Chemistry. 41(No.5). 1170-1176 (2001)

Tetsuaki Fujihara 等人：“新型蒽电子桥接钼锌卟啉二聚体的合成、性质和晶体结构”无机化学。

Hideki Sugimoto: "Comparative Structural, Spectrophotometric and Redox Studies of Isostructural Complexes of Ruthenium(III), Osmium(III), and Rhenium(III) : cis-Dichloro Complexes Containing Tris(2-pyridylmethyl)amine and Its 6-Methylpyridyl Derivative"Bu

Hideki Sugimoto：“钌 (III)、锇 (III) 和铼 (III) 的同构配合物的比较结构、分光光度和氧化还原研究：含有三(2-吡啶基甲基)胺及其 6-甲基吡啶基衍生物的顺式二氯配合物”

Ai Itasaka: "Octahedral Arrangement of Porphyrin Moieties around the Hexarhenium(III) Cluster Core. Crystal Structire of (μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-tritolyl-porphyrin)hexarhenium(III)(2+)"Angewandte Chemic, International Edition. 41(No.4).

板坂爱：“六铼(III)簇核周围卟啉部分的八面体排列。(μ_3-硒基)六(5-(4-吡啶基)-10,15,20-三甲苯基-卟啉)六铼(III)的晶体结构(2+)“Angewandte Chemic，国际版。41（No.4）。

Ai Itasaka, et al.: "Octahedral Arrangement of Porphyrin Moieties around the Hexarhenkium(III) Cluster Core. Crystal Structure of (μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-trirolylporphyrin)hexarheniurn(III) (2+)"Angewandte Chemie, International Edition.

Ai Itasaka 等人：“六芳基 (III) 簇核周围卟啉部分的八面体排列。(μ_3-Selenido)hexa(5-(4-pyridyl)-10,15,20-trirolylporphyrin)hexarheniurn 的晶体结构( III) (2+)“Angewandte Chemie，国际版。

Tetsuaki Fujihara: "Synthesis, Properties and Crystal Structure of a Novel Anthracene-Bridged Mo-Zn Porphyrin Dimer"Inorganic Chemistry. 41(5). 1170-1176 (2002)

Tetsuaki Fujihara：“新型蒽桥钼锌卟啉二聚体的合成、性质和晶体结构”无机化学。