Redox-Triggered Helicity Inversion in Chiral Cobalt Complexes in Combination with H<sup>+</sup> and NO<sub>3</sub><sup>–</sup> Stimuli
作者:Janusz Gregoliński、Masahiro Hikita、Tatsuya Sakamoto、Hideki Sugimoto、Hiroshi Tsukube、Hiroyuki Miyake
DOI:10.1021/acs.inorgchem.5b01902
日期:2016.1.19
in the presence of an organic base. Although the prepared cobalt(III) complexes were very inert and kinetically stable against protonation and NO3– complexation, cobalt(III) reduction in the presence of CF3SO3H and/or Bu4NNO3 allowed immediate changing of their three-dimensional structures from the contracted-Λoxo form to the extended-Λ [Co(H2L)Y2]n+ (Y = solvent and/or anion, n = 0–2) form with left-handed
作为先前报道的类似物,新合成了三种具有可变密度的手性配体H 2 L2- H 2 L4,它们分别与N,N′-亚乙基双[ N-甲基-(S)-丙氨酸]和邻杂取代的芳族胺共轭。H 2 L1。四收缩-Λ氧代钴(III)配合物[CO(大号)] +与Λ的左手螺旋结构4 Δ 2结构通过相应的收缩-Λ的单电子氧化,制备红钴(II)络合物[CO (L)],它们是在有机碱存在下由手性配体和Co(ClO 4)2 ·6H 2 O或Co(CF 3 SO 3)2 ·5.2H 2 O生成的。虽然制备的钴(III)配合物是非常惰性的并且动力学稳定对抗质子化和NO 3 -络合,钴(III)还原在CF的存在3 SO 3 H和/或卜4 NNO 3允许他们的三维的即时变化从收缩-Λ三维结构氧代形式到扩展-Λ[CO(H 2大号)Y 2] n +(Y =溶剂和/或阴离子,n = 0–2)形式为左旋螺旋,或扩展为Δ[Co(H 2 L)(NO