A proton-responsive ligand becomes a dimetal linker for multisubstrate assembly via nitrate deoxygenation
A proton-responsive ligand becomes a dimetal linker for multisubstrate assembly via nitrate deoxygenation
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DOI：
10.1039/d0cc07886g
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发表时间：
2021-03-18
影响因子：
4.9
通讯作者：
Caulton, Kenneth G.
中科院分区：
文献类型：
--
作者：
Cabelof, Alyssa C.;Carta, Veronica;Caulton, Kenneth G.
在二价镍上引入了一个双齿吡唑吡啶配体（HL），得到[（HL）（2）Ni（NO3）]NO3。该化合物与双甲硅烷基化的杂环，1，4-双-（三甲基甲硅烷基）-1，4-二氮杂-2，5-环己二烯（TMS（2）Pz）反应，同时还原一个硝酸根配体并使一个HL配体去质子化，得到八面体（HL）（L-）Ni（NO3）。形成的单硝酸盐物种然后进一步与TMS（2）Pz反应以双重脱硝硝酸盐并形成[（L-）Ni（NO）]（2），其通过具有弯曲的亚硝酰基配体的吡唑盐桥接而形成二聚体，代表配位硝酸盐的双电子还原。报道了一种二聚物[（L-）Ni（Br）]（2）的独立合成，它能有效地组装两种具有更好原子经济性的金属。
A bidentate pyrazolylpyridine ligand (HL) was installed on divalent nickel to give [(HL)(2)Ni(NO3)]NO3. This compound reacts with a bis-silylated heterocycle, 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (TMS(2)Pz) to simultaneously reduce one of the nitrate ligands and deprotonate one of the HL ligands, giving octahedral (HL)(L-)Ni(NO3). The mononitrate species formed is then further reacted with TMS(2)Pz to doubly deoxygenate nitrate and form [(L-)Ni(NO)](2), dimeric via bridging pyrazolate with bent nitrosyl ligands, representing a two-electron reduction of coordinated nitrate. Independent synthesis of a dimeric species [(L-)Ni(Br)](2) is reported and effectively assembles two metals with better atom economy.