Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics,Inorganic Chemistry

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Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00045
Henry H. Wilson ₁ , Connor A. Koellner ₂ , Zain M. Hannan ₁ , Caroline B. Endy ₂ , Mark W. Bezpalko ₃ , Nicholas A. Piro ₃ , W. Scott Kassel ₃ , Matthew D. Sonntag ₂ , Christopher R. Graves ₁

Affiliation

The synthesis and full characterization of a series of neutral ligand α-diimine complexes of aluminum are reported. The compounds [Al(L_Ar)₂Cl₂)][AlCl₄] [L_Ar = N,N′-bis(4-R-C₆H₄)-2,3-dimethyl-1,4-diazabutadiene] are structurally analogous, as determined by multinuclear NMR spectroscopy and solid-state X-ray diffraction, across a range of electron-donating [R = Me (2), ^tBu (3), OMe (4), and NMe₂ (5)] and electron-withdrawing [R = Cl (6), CF₃ (7), and NO₂ (8)] substituents in the aryl side arm of the ligand. UV–vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties, respectively, of the complexes. Both sets of properties are shown to be dependent on the R substituent. Density functional theory calculations performed on the [Al(L_Ph)₂Cl₂)][AlCl₄] complex (1) indicate primarily ligand-based frontier orbitals and were used to help support our discussion of both the spectral and electrochemical data. We also report the reaction of the L_Ph ligand with both AlBr₃ and AlI₃ and demonstrate a different reactivity profile for the heavier halide relative to the lighter members of the group.

中文翻译：

具有可调氧化还原能的铝的中性配体α-二胺配合物的合成与表征

报道了一系列铝的中性配体α-二亚胺配合物的合成和完整表征。化合物[Al（L _Ar）₂ Cl ₂）] [AlCl ₄ ] [L _Ar = N，N'-双（4-RC ₆ H ₄）-2,3-二甲基-1,4-二氮杂丁二烯]在结构上通过多核NMR光谱法和固态X射线衍射测定，在给电子体的整个范围内类似[R = Me（2），^t Bu（3），OMe（4）和NMe ₂（5）]和吸电子[R = Cl（6），CF ₃（7）和NO ₂（8）]取代基在配体的芳基侧臂中。紫外可见吸收光谱和电化学分别用于检测配合物的光学和电化学性质。两组性能均显示为取决于R取代基。在[Al（L _Ph）₂ Cl ₂）] [AlCl ₄ ]配合物（1）上进行的密度泛函理论计算主要表明基于配体的前沿轨道，并用于帮助支持我们对光谱和电化学数据的讨论。我们还报告了L _Ph配体与两种AlBr的反应_图3和A1 ₃示出了较重的卤化物相对于组中较轻的成员的不同反应性曲线。

更新日期：2018-03-19

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