Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, IN 47401, USA.
Chem Commun (Camb). 2021 Mar 16;57(22):2780-2783. doi: 10.1039/d0cc07886g.
A bidentate pyrazolylpyridine ligand (HL) was installed on divalent nickel to give [(HL)2Ni(NO3)]NO3. This compound reacts with a bis-silylated heterocycle, 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (TMS2Pz) 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 TMS2Pz 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.
二齿吡唑基吡啶配体 (HL) 被安装在二价镍上，得到 [(HL)2Ni(NO3)]NO3。该化合物与双硅烷基化杂环 1,4-双-(三甲基硅基)-1,4-二氮杂-2,5-环己二烯 (TMS2Pz) 反应，同时还原一个硝酸根配体并去质子化一个 HL 配体，得到八面体 (HL)(L-)Ni(NO3)。然后，形成的单硝酸根物种进一步与 TMS2Pz 反应，双重脱氧硝酸根并形成 [(L-)Ni(NO)]2，通过桥接吡唑盐与弯曲的亚硝酰配体形成二聚体，代表配位硝酸根的两电子还原。还报道了二聚体 [(L-)Ni(Br)]2 的独立合成，并有效地通过更好的原子经济性组装两个金属。
