Synthesis and Reactivity of Copper(I) Complexes Based on C3‐Symmetric Tripodal HTIM(PR2)3 Ligands,European Journal of Inorganic Chemistry

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Synthesis and Reactivity of Copper(I) Complexes Based on C3‐Symmetric Tripodal HTIM(PR2)3 Ligands
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2018-05-06 , DOI: 10.1002/ejic.201800074
Ekaterina S. Smirnova ₁ , Ferran Acuña-Parés ₁ , Eduardo C. Escudero-Adán ₁ , Christian Jelsch ₂ , Julio Lloret-Fillol _{1,

3}

Affiliation

We present the first example of non‐classical hydrogen bonding in Cu^I complexes. To this end, we have studied the coordination capacity of the tripodal phosphine ligands HTIM(PR₂)₃ {tris[1‐(di‐R‐phosphanyl)‐3‐methyl‐1H‐indol‐2‐yl]methane, R = Ph, iPr} towards copper, leading to a series of eight Cu^I complexes [{HTIM(PR₂)₃}CuX] [R = Ph (1–4), iPr (5–8); X = Cl^–, I^–, OTf^–, BF₄^–]. An anagostic interaction in the Cu^I complexes has been proposed based on the results of ¹H NMR, ultrahigh‐resolution X‐ray diffraction, and theoretical [atoms‐in‐molecules (AIM) and natural bonding orbital (NBO)] analyses of the electron density. Among the different synthesized complexes, [{HTIM(PPh₂)₃}CuOTf] (2) shows the strongest Cu···H–C interaction with a linear geometry (179.98°) and the shortest distance described so far [d(Cu–H) = 1.9 Å] in its toluene solvated form. Both parameters are characteristic of 3c–4e^– interactions. In addition, we have found that these tripodal ligands exhibit unprecedented selectivity towards Cu^I ions. The synthesized HTIM(PR₂)₃Cu^I complexes have been found to be catalytically active and selective for the hydroboration of CO₂ to formic acid.

中文翻译：

基于C3对称三脚架HTIM（PR2）3配体的铜（I）配合物的合成和反应性

我们提出了Cu ^I络合物中非经典氢键的第一个例子。为此，我们研究了三脚架膦配体HTIM（PR ₂）₃ {tris [1-（di-R-phosphanyl）-3-methyl-1 H-吲哚-2-yl]甲烷，R = Ph，i Pr}朝向铜，导致一系列八个Cu ^I络合物[{HTIM（PR ₂）₃ } CuX] [R = Ph（1-4），i Pr（5-8）; X = Cl ^–，I ^–，OTf ^–，BF ₄^– ]。Cu ^I中的无声相互作用根据¹ H NMR，超高分辨率X射线衍射以及电子密度的理论[分子内原子（AIM）和自然键合轨道（NBO）]分析，提出了配合物。在不同的合成配合物中，[{HTIM（PPh ₂）₃ } CuOTf]（2）显示出最强的Cu ··· H–C相互作用，具有线性几何形状（179.98°），并且是迄今为止描述的最短距离[ d（Cu -H）= 1.9Å]，呈甲苯溶剂化形式。这两个参数是3C-4E的特点^-互动。此外，我们发现这些三脚架配体对Cu ^I离子表现出空前的选择性。合成的HTIM（PR₂）已经发现_3种Cu ^I配合物具有催化活性，并且对于CO ₂加氢硼化成甲酸具有选择性。

更新日期：2018-05-06

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