Synthesis and characterization of aluminum nitroxide complexes
Synthesis and characterization of aluminum nitroxide complexes
复制标题
氮氧铝配合物的合成与表征
DOI：
10.1016/j.poly.2015.12.005
复制
发表时间：
2016
期刊：
影响因子：
2.6
通讯作者：
C. Graves
中科院分区：
文献类型：
--
作者：
Thomas M. Herb;Andrew M. Poitras;K. Richardson;Bren E. Cole;Justin A. Bogart;P. Carroll;E. Schelter;C. Graves
我们报道了吡啶基氮氧化物（RpyNO−）配体的铝配合物的合成。通过吡啶基羟胺配体RpyNOH与三甲基铝的1：1反应，合成了二聚体配合物{（μ-pyNO−）Al（CH 3）2}2（1）和{（μ-CH 3 pyNO −）Al（CH 3）2}2（2）.两种化合物均经1H和13 C NMR谱表征。X射线结构分析表明，1和2是同构的，二聚体结构由一个Al 2 O2核形成。pyNOH与2当量的三甲基铝反应生成铝配合物（pyNO−）AlMe 2·AlMe 3（3），并通过1H和13 C NMR谱和单分子X射线衍射对其进行了表征。用紫外-可见吸收光谱和电化学方法研究了{（μ-pyNO−）Al（CH 3）2} 2和{（μ-CH 3 pyNO −）Al（CH 3）2} 2配合物的电子结构.配合物的循环伏安图显示了两个独立的氧化过程，其电位都取决于RpyNO −配体的取代模式。
We report the synthesis of aluminum complexes of pyridyl nitroxide (RpyNO−) ligands. The dimeric complexes {(μ-pyNO−)Al(CH3)2}2(1) and {(μ-CH3pyNO−)Al(CH3)2}2(2) were prepared through the 1:1 reaction between the pyridyl hydroxylamine ligand precursorsRpyNOH and trimethylaluminum. Both compounds were characterized by1H and13C NMR spectroscopies. X-ray structural analysis revealed that1and2are isostructural, with the dimer structure resulting from an Al2O2core. Reaction of pyNOH with two equivalents of trimethylaluminum yielded the aluminum complex (pyNO−)AlMe2·AlMe3(3), which was also characterized by1H and13C NMR spectroscopies and single-molecule X-ray diffraction. The electronic structure of the {(μ-pyNO−)Al(CH3)2}2and {(μ-CH3pyNO−)Al(CH3)2}2complexes were interrogated using UV–Vis electronic absorption spectroscopy and electrochemistry. The cyclic voltammograms of the complexes show two separate oxidation processes, the potentials of which are both dependent on the substitution pattern of theRpyNO−ligands.