Synthesis,structure and electrochemical properties of a group of ruthenium(III) complexes of N-(aryl)picolinamide

Anindya Das; Shie-Ming Peng; Gene-Hsiang Lee; Samaresh Bhattacharya

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Synthesis,structure and electrochemical properties of a group of ruthenium(III) complexes of N-(aryl)picolinamide

机译：N-（芳基）吡啶甲酸酰胺的钌（III）配合物的合成，结构和电化学性能

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Reaction of N-(aryl)picolinamide (HL-R;R=OCH_3,CH_3,H,Cl and NO_2) with ruthenium trichloride or [Ru(DMSO)_4Cl_2] in refluxing 2-methoxyethanol in the presence of a base (NEt_3) affords tris complexes of the type [Ru(L-R)_3].The structure of the [Ru(L-OCH_3)_3] complex has been determined by X-ray crystallography.In these complexes the amide ligands are coordinated to the metal center as monoanionic bidentate N,N-donors.All the [Ru(L-R)_3] complexes are one-electron paramagnetic and show rhombic ESR spectra at 77 K.They also show intense LMCT transitions in the visible region.Cyclic voltammetry on all the complexes shows a ruthenium(III)/ruthenium(IV) oxidation within the range of 0.89 to 1.21 V vs.SCE and a ruthenium(III)/ruthenium(II) reduction within the range of-0.22 to-0.41 V vs.SCE.Representative one-electron oxidized and reduced complexes,viz.[Ru~(IV)(L-H)_3]~+ and [Ru~(II)(L-H)_3]~-,respectively,have also been generated in solution and characterized spectroscopically as well as electrochemically.

机译：N-（芳基）吡啶啉酰胺（HL-R; R = OCH_3，CH_3，H，Cl和NO_2）与三氯化钌或[Ru（DMSO）_4Cl_2]在2-甲氧基乙醇中在碱（NEt_3）回流下反应得到[Ru（LR）_3]类型的tris配合物。[Ru（L-OCH_3）_3]配合物的结构已通过X射线晶体学测定。在这些配合物中，酰胺配体与金属中心配位为单阴离子双齿N，N供体。所有[Ru（LR）_3]配合物均为单电子顺磁性，在77 K处显示菱形ESR谱。它们在可见光区域也显示出强烈的LMCT跃迁。所有配合物的循环伏安法表明相对于SCE，钌（III）/钌（IV）的氧化范围为0.89至1.21 V;相对于SCE，钌（III）/钌（II）的还原度范围为-0.22至-0.41 V. -电子氧化和还原的配合物，即[Ru〜（IV）（LH）_3]〜+和[Ru〜（II）（LH）_3]〜-，也分别在溶液中生成并进行了光谱表征如电化学的。

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《New Journal of Chemistry》 |2004年第6期|共6页
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Anindya Das; Shie-Ming Peng; Gene-Hsiang Lee; Samaresh Bhattacharya;
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Synthesis,structure and electrochemical properties of a group of ruthenium(III) complexes of N-(aryl)picolinamide

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