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.

低急症配体定义为一种配体，其中将最大可能数量的供体原子粘结到金属中心的配体。该研究的目的是准备包含此类配体的各种新复合物，并研究其重复性和功能特征。特别是，我们特别关注光子复合物，因为使用不协调的配体部分可以控制光物理特性。通过使用多吡啶基配体（例如Tris（2-吡啶基甲基）胺（TPA）和N，N，N，N'，N'，N'Tetrakis（2-吡啶基甲基）乙二胺（TPEN）获得的结果，如下所示，如下所示，（I）一系列Planar Pt（II）和PD（II）和PD（II）和这些Ligigss confcords and unc unc unc unc unc unc unc unc。在pt（ii）<pd（ii）和tpa <tpen的顺序中发现了自由和协调的臂的交换。 （ii）制备了发光[re（co）_3（co）_3（tpa）]^+，它还具有一个不与协调的臂不交换的不协调的臂。 （iii）TPA的V^<iv> O复合物具有完全协调的TPA（四元），与具有三叉戟TPA的REO-TPA复合物不同，但具有TPEN V^<iv> o，含有含有低急症配体的tpen v^<iv> o。使用双磷蛋白配体PH_2P（CH_2）_NPPH_2（n = 1-5），已经获得了一系列含有单次谐二磷酸的发光六边形簇簇复合物。对于六边形单元，我们还成功地引入了巨大的配体吡啶基孢子。我们还使用了一个小的多脱牙配体，2.5-二甲虫-1,3,4-噻二唑（MCMTH）。制备的复合物包括包含单次MCMT的复合物为[pt（terpy）（mcmt）]^+和[ru（terpy）（bpy）（mcmt）（mcmt）]^+。他们与另一个PT（Terpy）单位反应，形成同性恋和杂核综合体。此外，已经获得了MCMT配体的各种类型的Cu（I）和Ag（I）复合物。所有这些MCMT复合物都非常发光。

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, 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。

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）。

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。