Redox Series of Cyclometalated Nickel Complexes [Ni((R)Ph(R′)bpy)Br]+/0/–/2– (H–(R)Ph(R′)bpy = Substituted 6-Phenyl-2,2′-bipyridine)
Redox Series of Cyclometalated Nickel Complexes [Ni((R)Ph(R′)bpy)Br]+/0/–/2– (H–(R)Ph(R′)bpy = Substituted 6-Phenyl-2,2′-bipyridine)
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DOI：
10.1021/acs.organomet.8b00559
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发表时间：
2018-09
期刊：
影响因子：
2.8
通讯作者：
Aaron Sandleben;Nicolas Vogt;G. Hörner;A. Klein
中科院分区：
文献类型：
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作者：
Aaron Sandleben;Nicolas Vogt;G. Hörner;A. Klein
以前体[Ni(COD)2] （COD = 1,5-环二烯）和原配体（配体前体）Br -(R)Ph(R ')bpy)为原料，合成了新的有机镍配合物[Ni((R)Ph(R ')bpy)Br]，其携带三齿c∧N∧N配体6-（苯基-2-ide）-2,2 ' -联吡啶（- Phbpy）的各种取代衍生物。对原配基的几种合成路线进行了研究和比较。所有的新化合物都经过了分析和光谱表征。通过XRD实验得到了不同配合物的晶体结构和分子结构。紫外-可见吸收光谱和详细的电化学测量揭示了各种取代基对配合物电子结构的影响。量子化学DFT计算说明了最高已占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）的组成，并支持了单电子还原和氧化产物作为双定域配体自由基和瞬态镍（III）中间体的分配。
New organonickel complexes [Ni((R)Ph(R′)bpy)Br] carrying various substituted derivatives of the tridentate –C∧N∧N ligand 6-(phenyl-2-ide)-2,2′-bipyridine (−Phbpy) were synthesized from the precursor [Ni(COD)2] (COD = 1,5-cyclooctadiene) and the protoligands (ligand precursors) Br–(R)Ph(R′)bpy. Several synthetic routes for the protoligands were studied and compared. All new compounds have been analyzed and spectroscopically characterized. From several complexes crystal and molecular structures were obtained from XRD experiments. UV–vis absorption spectroscopy and detailed electrochemical measurements reveal the impact of the various substituents on the electronic structure of the complexes. Quantum chemical DFT calculations illustrate the composition of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) and support the assignment of the single-electron reduction and oxidation products as bpy-localized ligand radical species and transient nickel(III) intermediates, re...