Synthesis and Characterization of Ruthenium(II)-Nitrile Complexes with Bisamide-tpa Ligands(tpa = Tris(2-pyridylmethyl)amine)

Takahiko Kojima; Ken-ichi Hayashi; Yoshihito Shiota; Yoshimitsu Tachi; Yoshinori Naruta

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Synthesis and Characterization of Ruthenium(II)-Nitrile Complexes with Bisamide-tpa Ligands(tpa = Tris(2-pyridylmethyl)amine)

机译：双酰胺-tpa配体（tpa =三（2-吡啶基甲基）胺）钌（II）-腈配合物的合成与表征

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Ruthenium(II)-acetonitrile complexes having pentadentate tris(2-pyridylmethyl)amine(tpa)derivatives with coordinated amide CO groups were prepared and characterized by various spectroscopic methods,electrochemical measurements,and DFT calculations.The acetonitrile ligand was indicated to tightly bind to the ruthenium(II)center in an eta~1-N fashion.The Mulliken charge distribution,obtained by a calculation,indicated that the ruthenium(II)-nitrile bond is more covalent than other coordination bonds of the tpa moiety.The redox potentials of Ru centers and the chemical shifts of methyl groups of the acetonitrile ligands exhibited a linear relationship,indicating that electron density of the Ru center controls that of the acetonitrile ligand.Those complexes showed fluxional behavior in CD_3CN solutions to exhibit one mode of thermal motion;it also altered the symmetry of the complexes.

机译：制备了具有配位酰胺CO基团的五齿三（2-吡啶甲基甲基）胺（tpa）衍生物的钌（II）-乙腈配合物，并通过各种光谱方法，电化学测量和DFT计算对其进行了表征。表明乙腈配体紧密结合通过计算获得的Mulliken电荷分布表明，钌（II）-腈键比tpa部分的其他配位键更共价。钌中心的电子化与乙腈配体的甲基的化学位移呈线性关系，表明钌中心的电子密度控制着乙腈配体的电子密度。这些络合物在CD_3CN溶液中表现出通量行为，表现出一种热运动。它也改变了配合物的对称性。

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《Bulletin of the Chemical Society of Japan》 |2005年第12期|共7页
作者
Takahiko Kojima; Ken-ichi Hayashi; Yoshihito Shiota; Yoshimitsu Tachi; Yoshinori Naruta;
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中图分类化学;
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1. Synthesis and Characterization of Ruthenium(II)-Nitrile Complexes with Bisamide-tpa Ligands(tpa = Tris(2-pyridylmethyl)amine) [J] . Takahiko Kojima, Ken-ichi Hayashi, Yoshihito Shiota, Bulletin of the Chemical Society of Japan . 2005,第12期

机译：双酰胺-tpa配体（tpa =三（2-吡啶基甲基）胺）钌（II）-腈配合物的合成与表征
2. The preparation and full characterization of dichloroferrous complexes of mono-, bis- and tris-alpha-methyl substituted tris(2-pyridylmethyl)amine (TPA) ligands. Structural bases of stability of the complexes in solution [J] . Benhamou L, Lachkar M, Mandon D, Dalton transactions: An international journal of inorganic chemistry . 2008,第48期

机译：单，双和三-α-甲基取代的三（2-吡啶基甲基）胺（TPA）配体的二氯亚铁配合物的制备和完整表征。溶液中配合物稳定性的结构基础
3. Synthesis and characterization of mononuclear and dinuclear ruthenium complexes with tris(2-pyridylmethyl)amine and tris(5-methyl-2-pyridylmethyl)amine [J] . Kojima T., Ishii Y., Ohba M., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1998,第16期

机译：三（2-吡啶基甲基）胺和三（5-甲基-2-吡啶基甲基）胺的单核和双核钌配合物的合成与表征
4. RUTHENIUM(II) TRIS-BIPYRIDINE COMPLEXES WITH A 60FULLERENE LIGAND: SYNTHESIS AND PROPERTIES [C] . Michele Maggini, Enzo Menna, Giorgia Possamai, International Symposium on Fullerenes, Nanotubes, and Carbon Nanoclusters, Mar, 25-29, 2001, Washington, D.C. . 2001

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5. Structural characterization of iron(III) tris(2-pyridylmethyl)amine complexes with the formulas (iron(TPA)X(2))(chlorine tetroxide) and ((iron(TPA)X)(2)O)(chlorine tetroxide)(2). [D] . Xue, Jia. 1996

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7. Cobalt(II) tris(2-pyridylmethyl)amine complexes [Co(TPA)X](+) bearing coordinating anion (X = Cl-, Br-, I- and NCS-): synthesis and application for carbon dioxide reduction [O] . Chan, SLF, Lam, TL, Yang, C, 2017

机译：带有配位阴离子（X = Cl-，Br-，I-和NCS-）的钴（II）三（2-吡啶基甲基）胺配合物[Co（TPA）X]（+）：合成和用于二氧化碳还原

Synthesis and Characterization of Ruthenium(II)-Nitrile Complexes with Bisamide-tpa Ligands(tpa = Tris(2-pyridylmethyl)amine)

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