Macrocyclic Aryl–Nickel(II) Complexes: Synthesis, Structure, and Reactivity Studies
Macrocyclic Aryl–Nickel(II) Complexes: Synthesis, Structure, and Reactivity Studies
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大环芳基-镍(II)配合物：合成、结构和反应性研究
DOI：
10.1021/acs.organomet.5b00733
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发表时间：
2015
期刊：
影响因子：
2.8
通讯作者：
Mei
中科院分区：
文献类型：
--
作者：
Chi Yang;Wen;Liang Zhao;Mei
通过两个大环氮杂杯[m]芳烃[n]吡啶配体的直接亲电金属化反应，合成了单芳基镍（II）化合物2和二芳基镍（II）化合物4，并对其进行了表征和反应活性研究。化合物4在质子溶剂和酸中比单芳基-Ni（II）化合物2稳定得多。此外，2可以与各种亲核试剂反应，导致形成C-C，C-O，C-Br和C-N键。相反，化合物4在与大量亲核试剂反应时表现出非常惰性的反应性。有趣的是，化合物2也能够与几种体积较小的烷基卤化物反应形成新的C-C键，而相同的程序不适用于4。在这项工作中报告的研究提供了一个彻底的调查芳基镍（II）物种的反应性，应促进镍催化的C-H官能化的详细机制的理解。
The synthesis, characterization, and reactivity of the monoaryl–Ni(II) compound 2 and the diaryl–Ni(II) compound 4 formed through the direct electrophilic metalation of two macrocyclic azacalix[m]arene[n]pyridine ligands are described. Compound 4 was much more stable in protic solvents and acids than the monoaryl–Ni(II) compound 2. Moreover, 2 can react with a variety of nucleophiles, resulting in the formation of C–C, C–O, C–Br, and C–N bonds. In contrast, compound 4 exhibited very inert reactivity upon reaction with a large numberof nucleophiles. Interestingly, compound 2 was also capable of reacting with several less bulky alkyl halides to form new C–C bonds, while the same procedure is inapplicable to 4. The study reported in this work provides a thorough investigation on the reactivity of aryl–Ni(II) species that should facilitate comprehension of the detailed mechanism of nickel-catalyzed C–H functionalization.
影响因子：
62.1
作者：
Rosen, Brad M.;Quasdorf, Kyle W.;Wilson, Daniella A.;Zhang, Na;Resmerita, Ana-Maria;Garg, Neil K.;Percec, Virgil
通讯作者：
Percec, Virgil
影响因子：
15
作者：
Ge, Shaozhong;Hartwig, John F.
通讯作者：
Hartwig, John F.
影响因子：
4.9
作者：
Koch, Eva;Takise, Ryosuke;Itami, Kenichiro
通讯作者：
Itami, Kenichiro