Nitrogen–Nitrogen Bond Formation via a Substrate-Bound Anion at a Mononuclear Nickel Platform

Nitrogen–Nitrogen Bond Formation via a Substrate-Bound Anion at a Mononuclear Nickel Platform
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DOI:
10.1021/acs.organomet.7b00887
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发表时间:
2018-02
期刊:
影响因子:
2.8
通讯作者:
M. Kosobokov;Aaron Sandleben;Nicolas Vogt;A. Klein;David A. Vicic
M. Kosobokov;Aaron Sandleben;Nicolas Vogt;A. Klein;David A. Vicic
中科院分区:
化学2区
文献类型:
--
作者:
M. Kosobokov;Aaron Sandleben;Nicolas Vogt;A. Klein;David A. Vicic

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镍-C4 F8片段与氨基芳基N-H酮亚胺配位形成稳定的络合物,其在用碱和氧化剂处理时导致N-N键形成反应和吲唑产物的释放。一个关键的和以前未确定的中间体形成的吲唑是一个二亚胺配合物的镍轴承上的芳基环,最初含有胺取代基的显着电荷。C4 F8共配体是氧化还原转化和稳定中间体以进行表征的关键。
The nickel-C4F8 fragment coordinates an aminoaryl N–H ketimine to form a stable complex, which upon treatment with base and oxidant leads to an N–N bond-forming reaction and the release of indazole product. A key and previously unidentified intermediate in the formation of the indazole was a diimine complex of nickel bearing significant charge on the aryl ring that initially contained the amine substituent. The C4F8 coligand was key for the redox transformation and for stabilization of the intermediate for characterization.