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Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes

机译:在噻啶基铂(II)钳子复合物中调整两电子转移

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摘要

An important factor in obtaining reversible multi-electron transfer is overcoming large changes in coordination geometry. One strategy is to use ligands that can support the geometries favored before and after the electron transfer. Pip(2)NCN(-) pincer and terpyridine ligands are used to support square planar Pt(ii) and octahedral Pt(iv). For the Pt(ii) complexes, [Pt(Z-pip(2)NCN)(R-tpy)](+) (Z = NO2, MeO, H; R = H, tertyl butyl, tolyl), H-1 NMR spectroscopy shows that the Z-pip(2)NCN(-) ligand is monodentate whereas the R-terpyridyl ligand is tridentate. The availability of flanking piperidyl groups of the monodentate pincer ligand is essential for the stabilization of the metal center upon oxidation. Pt(Z-pip(2)NCN)(R-tpy)(+) complexes undergo two-electron platinum centered oxidation near 0.4 V and two Pt(tpy) centered reductions near -1.0 V and -1.5 V. An estimate of n(ox)/n(red) = 1.8 is consistent with an oxidation that involves two-electron transfer per Pt center. Variation in the pincer-(Z) and terpyridine-(R) substituents allows for tuning of the oxidation process over a 260 mV range and the two reduction processes over ranges of 230 mV (first reduction) and 290 mV (second reduction step).
机译:获得可逆多电子传输的一个重要因素克服了协调几何形状的大变化。一种策略是使用配体,这些配体可以支持电子转移前后青睐的几何形状。 PIP(2)NCN( - )钳子和萜烯配体用于支撑方形平面Pt(II)和八面体Pt(IV)。对于Pt(II)配合物,[Pt(Z-PIP(2)NCN)(R-TPY)](+)(Z = NO2,MEO,H; R = H,叔丁基,甲苯基),H-1 NMR光谱表明,Z-PIP(2)NCN( - )配体是单址,而R-Terpyridyl配体是三齿。单常液钳配体的侧翼哌啶基的可用性对于氧化时稳定金属中心是必不可少的。的Pt(Z-PIP(2)NCN)(R-TPY)(+)的复合物经历两电子铂中心氧化近0.4伏和两个铂(TPY)为中心附近降低-1.0 V和-1.5的n V的估计(牛)/ n(红色)= 1.8与涉及每PT中心的两电子传递的氧化一致。变化在pincer-(Z)和terpyridine-(R)取代基允许在一个260毫伏范围的氧化过程的调谐和超过230毫伏(第一还原)和290毫伏(第二还原步骤)的范围内的两个还原过程。

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  • 来源
    《RSC Advances》 |2019年第37期|共9页
  • 作者单位

    Univ Cincinnati Dept Chem 2600 Clifton Ave Cincinnati OH 45221 USA;

    Case Western Reserve Univ Dept Chem 10900 Euclid Ave Cleveland OH 44106 USA;

    Univ Cincinnati Dept Chem 2600 Clifton Ave Cincinnati OH 45221 USA;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

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