Formation of Iridium(III) Complexes via Selective Activation of the C-H and N-H Bonds of a Dipyridylpyrrole Ligand.,Inorganic Chemistry

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Formation of Iridium(III) Complexes via Selective Activation of the C-H and N-H Bonds of a Dipyridylpyrrole Ligand.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-08 , DOI: 10.1021/acs.inorgchem.9b02560
Meng Xue ₁ , Dan-Ling Zhuang ₂ , Hao Li ₁ , Piao He ₁ , Chao Liu ₁ , Jun Zhu ₂ , Xiao-Yi Yi ₁

Affiliation

Treatment of [Ir(PPh3)3Cl] with 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine (Hdpp) in refluxing toluene affords an unexpected pyrrole-metalated iridium(III) hydride complex, [Ir(K2C,N-dpp)(H)(Cl)(PPh3)2] (1), via Cpyrrole-H activation, while the presence of the base KOtBu as the deprotonation reagent produces a pyridine-metalated iridium(III) hydride complex, [Ir(K3C,N,N-dpp)(H)(PPh3)2] (2), via Cpyridine-H activation. Treatment of [Ir(PPh3)3Cl] prepared by a convenient method with Hdpp in the presence of KOtBu under the refluxing mixture solvent toluene/methanol (2:1, v/v) generates the N,N-chelating complex [Ir(K2N,N-dpp)(H)(Cl)(PPh3)2] (3) together with 1 and the N,N-chelating dihydride complex [Ir(K2N,N-dpp)(H)2(PPh3)2] (4). Complex 4 is also readily produced by the reaction of [Ir(PPh3)3Cl] and Hdpp in the presence of KOtBu under refluxing methanol or by the reaction of IrCl3 and PPh3 in refluxing 2-ethoxyethanol. Complexes 1-4 are fully characterized by NMR, IR, and UV-vis spectroscopy and X-ray diffraction analysis. The dpp-/dpp2- ligand shows rich coordination capability, of which pyridine- and pyrrole-cyclometalated coordination modes are first reported. The formation of structural isomers 1 and 3 involved the selective activation of the C-H and N-H bonds of Hdpp is rationalized by theoretical calculations.

中文翻译：

通过选择性地活化双吡啶基吡咯配体的CH和NH键形成铱（III）配合物。

在回流的甲苯中用2- [5-（吡啶-2-基）-1H-吡咯-2-基]吡啶（Hdpp）处理[Ir（PPh3）3Cl]得到意外的吡咯金属化铱（III）氢化物络合物，[Ir（K2C，N-dpp）（H）（Cl）（PPh3）2]（1），通过Cpyrrole-H活化，同时存在碱KOtBu作为去质子化试剂时，会生成吡啶金属化的铱（III））氢化物络合物[Ir（K3C，N，N-dpp）（H）（PPh3）2]（2），通过吡啶-H激活。在溶剂甲苯/甲醇（2：1，v / v）回流混合物中，在KOtBu存在下用Hdpp处理通过便利方法制备的[Ir（PPh3）3Cl]生成N，N-螯合配合物[Ir（K2N），N-dpp）（H）（Cl）（PPh3）2]（3）连同1和N，N-螯合二氢化物配合物[Ir（K2N，N-dpp）（H）2（PPh3）2]（ 4）。在KOtBu存在下，在回流甲醇中，[Ir（PPh3）3Cl]与Hdpp反应，或者在回流2-乙氧基乙醇中，通过IrCl3与PPh3反应，也很容易生成配合物4。配合物1-4通过NMR，IR和UV-可见光谱和X-射线衍射分析充分表征。dpp- / dpp2-配体显示出很强的配位能力，其中首先报道了吡啶和吡咯环金属化的配位模式。结构异构体1和3的形成涉及Hdpp CH和NH键的选择性激活是通过理论计算合理化的。首先报道了吡啶和吡咯环金属化的配位模式。结构异构体1和3的形成涉及Hdpp CH和NH键的选择性激活是通过理论计算合理化的。首先报道了吡啶和吡咯环金属化的配位模式。结构异构体1和3的形成涉及Hdpp CH和NH键的选择性激活是通过理论计算合理化的。

更新日期：2020-01-08

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