Nickel Perfluoroalkyl Complexes Supported by Simple Acetate Coligands
Nickel Perfluoroalkyl Complexes Supported by Simple Acetate Coligands
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DOI：
10.1021/acs.organomet.4c00029
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发表时间：
2024-03
期刊：
影响因子：
2.8
通讯作者：
Cherry Mae T. Ravidas;Scott T. Shreiber;Lukas Kletsch;Axel Klein;David A. Vicic
中科院分区：
文献类型：
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作者：
Cherry Mae T. Ravidas;Scott T. Shreiber;Lukas Kletsch;Axel Klein;David A. Vicic
通过19 F核磁共振光谱探索了醋酸四甲基铵与[（MeCN）2Ni（CF 3）2]、[（MeCN）2Ni（C2 F5）2]和[NMe 4][（MeCN）Ni（CF 3）3]的相互作用。我们表明，根据镍络合物的性质，一个或两个乙酸根配体可以添加到金属中心，并取代镍结合的MeCN配体，这取决于乙酸根浓度。可以结合到镍的乙酸酯的数量，以及所得到的复合物是否作为单体或二聚体存在，被确定为取决于氟烷基配体的性质。此外，我们观察到在两当量乙酸盐存在下[（MeCN）2Ni（CF3）2]的镍中心的氧化干净地导致八面体顺磁性（EPR光谱）和阴离子Ni（III）络合物[NMe4][Ni（CF3）2（OAc）2]。
The interaction of tetramethylammonium acetate with [(MeCN)2Ni(CF3)2], [(MeCN)2Ni(C2F5)2], and [NMe4][(MeCN)Ni(CF3)3] was explored by 19F NMR spectroscopy. We show that depending on the nature of the nickel complex, one or two acetate ligands can add to the metal center and replace the nickel-bound MeCN ligands, depending on the acetate concentration. The number of acetates that could bind to nickel, and whether the resulting complex exists as a monomer or dimer, was determined to be dependent on the nature of the fluoroalkyl ligand. Moreover, we observe that oxidation of the nickel center of [(MeCN)2Ni(CF3)2] in the presence of two equivalents of acetate leads cleanly to the octahedral, paramagnetic (EPR spectroscopy), and anionic Ni(III) complex [NMe4][Ni(CF3)2(OAc)2].