State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou 350002, China.
Inorg Chem. 2011 Mar 21;50(6):2191-8. doi: 10.1021/ic102181h. Epub 2011 Feb 18.
One-dimensional (1D) homochiral nickel coordination polymers Ni(3)(bpdc)(RR-L)(2)·(DMF) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and Ni(3)(bpdc)(SS-L)(2)·(DMF) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.
一维（1D）手性镍配合物聚合物Ni(3)(bpdc)(RR-L)(2)·(DMF) (2R, RR-L = (R,R)-(-)-1,2-环己二胺-N,N'-双(3-叔丁基-5-(4-吡啶基)水杨醛基))和Ni(3)(bpdc)(SS-L)(2)·(DMF) (2S, SS-L = (S,S)-(-)-1,2-环己二胺-N,N'-双(3-叔丁基-5-(4-吡啶基)水杨醛基)基于手性吡啶功能化水杨醛（Ni）金属配合物单元 NiL((1,2-环己二胺-N,N'-双(3-叔丁基-5-(4-吡啶基)水杨醛基))Ni(II)))已经被合成并通过微量分析、红外光谱、固态紫外-可见光谱、热重分析（TGA）、圆二色性（CD）光谱、循环伏安测量以及粉末和单晶 X 射线衍射进行了表征。每个 NiL 作为无桥接的悬垂金属配合物，使用一个末端吡啶基团来配位非手性单元（镍和 bpdc(2-)）构建螺旋链，而另一个吡啶基团保持未配位。2R 和 2S 都包含由非手性构建块组成的左旋和右旋螺旋链，而 NiL 作为远程外部手性源垂直于螺旋链的骨架。含有金属配合物 NiL 中不饱和活性镍中心的镍配位聚合物 2R 和 2S 可用作自支撑多相催化剂。它们在烯烃环氧化反应中表现出与均相对应物相当的催化活性，并显示出作为可回收催化剂的巨大潜力。
