The curious cases of tetrahydrosalen-type ligands interacting with Ni( ii ): structures and ligand-based oxidation reactions
The curious cases of tetrahydrosalen-type ligands interacting with Ni( ii ): structures and ligand-based oxidation reactions
复制标题
四氢salen型配体与Ni(ii)相互作用的奇怪案例：结构和基于配体的氧化反应
DOI：
10.1039/d3dt02023a
复制
发表时间：
2023
影响因子：
4
通讯作者：
Guan, Hairong
中科院分区：
文献类型：
--
作者：
Xu, Vivian;Pandey, Bedraj;Jayawardhena, J. P.;Krause, Jeanette A.;Guan, Hairong
本工作围绕两个四氢Salen型前配体N，N′-双（2-羟基苄基）邻苯二胺（H2salophan）和N，N′-双（2-羟基-3-甲基苄基）邻苯二胺（H2salophan_Me）的镍配合物展开。当加入NaOH辅助配体去质子化时，H2 salophan与Ni（OAc）2·4 H2O反应生成双核配合物Ni 2（Hsalophan）2（OAc）2或Na[Ni 2（salophan）2（OAc）]。H2 salophan_Me与Ni（OAc）2·4 H2O反应生成单核配合物Ni（Hsalophan_Me）2。与相应的salen型镍配合物不同，这些四氢salen型配合物是顺磁性的和空气敏感的（在溶液中）。通过O2或过氧化物的氧化导致配体骨架脱氢以形成Salen型络合物。
This work centers around the nickel complexes derived from two tetrahydrosalen-type proligands: N,N′-bis(2-hydroxybenzyl)-o-phenylenediamine (H2salophan) and N,N′-bis(2-hydroxy-3-methylbenzyl)-o-phenylenediamine (H2salophan_Me). The reaction of H2salophan with Ni(OAc)2·4H2O generates a dinuclear complex Ni2(Hsalophan)2(OAc)2 or Na[Ni2(salophan)2(OAc)] when NaOH is added to assist ligand deprotonation. The reaction of H2salophan_Me with Ni(OAc)2·4H2O, however, yields a mononuclear complex Ni(Hsalophan_Me)2. Unlike the corresponding salen-type nickel complexes, these tetrahydrosalen-type complexes are paramagentic and air sensitive (in solution). Oxidation by O2 or peroxides results in dehydrogenation of the ligand backbone to form the salen-type complexes.