Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland, Canada A1B 3X7.
Dalton Trans. 2010 Jan 14(2):548-59. doi: 10.1039/b910254j. Epub 2009 Oct 6.
Two lithium amine-bis(phenolate) and four chromium(III) amine-bis(phenolate) complexes have been prepared. The diprotonated tripodal tetradentate ligand precursors 2-tetrahydrofurfuryl-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol), H(2)O(2)NO; 2-tetrahydrofurfuryl-N,N-bis(2-methylene-4,6-tert-butylphenol), H(2)O(2)NO; 2-pyridylamino-N,N-bis(2-methylene-4,6-methylphenol), H(2)O(2)NN'; and 2-pyridylamino-N,N-bis(2-methylene-4,6-tert-butylphenol), H(2)O(2)NN'; can be lithiated using n-butyllithium. Isolation of the Li(2)O(2)NO compounds generates dimeric {Li(2)O(2)NO}(2) (R = t-Bu, R' = Me in 1 and R = R' = t-Bu in 2) in the solid state as shown by single-crystal X-ray diffraction. The lithiated ligands were used to prepare a series of Cr(III) complexes. Monometallic complexes are obtained when prepared and purified under strictly anhydrous conditions, giving CrCl(THF)O(2)NO (R = t-Bu, R' = Me in 3 and R = R' = t-Bu in 4). However, bimetallic Cr complexes are obtained upon recrystallization in air, where adventitious water reacts with the complex resulting in protonation of one of the phenolate groups of the ligand and generating hydroxide, which bridges two Cr(III) centres. Solid-state single-crystal X-ray diffraction studies of {CrClO(2)NN'}(mu-HO){CrClHO(2)NN'}, 5, and {CrClO(2)NN'}(mu-HO){CrClHO(2)NN'}, 6, were performed. The paramagnetic Cr(III) complexes were also characterized by UV-vis spectroscopy, mass spectrometry and magnetic measurements.
已经制备了两种锂胺双（邻苯二酚）和四种铬（III）胺双（邻苯二酚）配合物。双质子化的三脚四齿配体前体 2-四氢糠基-N,N-双（2-亚甲基-4-甲基-6-叔丁基苯氧基），H(2)O(2)NO; 2-四氢糠基-N,N-双（2-亚甲基-4,6-叔丁基苯氧基），H(2)O(2)NO; 2-吡啶基氨基-N,N-双（2-亚甲基-4,6-甲基苯氧基），H(2)O(2)NN'; 和 2-吡啶基氨基-N,N-双（2-亚甲基-4,6-叔丁基苯氧基），H(2)O(2)NN'; 可以使用正丁基锂进行锂化。分离 Li(2)O(2)NO化合物在固态中生成二聚体 {Li(2)O(2)NO}(2)（R = t-Bu，R' = Me 在 1 中，R = R' = t-Bu 在 2 中），如单晶 X 射线衍射所示。锂化配体用于制备一系列 Cr(III)配合物。在严格无水条件下制备和纯化时，得到单核配合物，得到 CrCl(THF)O(2)NO（R = t-Bu，R' = Me 在 3 中，R = R' = t-Bu 在 4 中）。然而，在空气中重结晶时得到双金属 Cr 配合物，其中偶然的水与配合物反应导致配体的一个邻苯二酚基团质子化，并生成氢氧化物，该氢氧化物桥接两个 Cr(III)中心。{CrClO(2)NN'}(mu-HO){CrClHO(2)NN'},5 和 {CrClO(2)NN'}(mu-HO){CrClHO(2)NN'},6 的固态单晶 X 射线衍射研究已经进行。顺磁 Cr(III)配合物也通过紫外可见光谱、质谱和磁性测量进行了表征。
