Synthesis of Solid-state Metal Phosphate Catalysts Having Chiral Structure

为了探索不对称有机合成中的手性固体催化剂，合成了不同结构的金属离子和有机胺阳离子的环己磷酸盐。对合成的晶体材料进行了结构表征。脂肪胺的有机阳离子对形成结构非常重要，因为被有机阳离子中和的单体环己磷酸根阴离子通过有机阳离子之间的氢键连接在一起，从而在结构中形成二维网络。当体系中存在金属阳离子时，金属阳离子起到连接环己磷酸根阴离子的作用，形成无限长的金属阳离子-环己磷酸根链，其中的正电荷被有机阳离子中和，形成三维网络结构，对[Cu（bpy）_2] [Cu（bpy）] [Cu（bpy）（py）]P_6O_（<18->10）H_（20）的结构分析表明，六偏磷酸根配合物是通过分子自组装结晶而成的。三种不同的Cu^2^-以不同的方式与六偏磷酸根阴离子的氧配位而存在。[Cu（bpy）_2]^&lt;2+&gt;的配位氧数为1个，[Cu（bpy）]^&lt;2 +&gt;为3个，[Cu（bpy）（py）]^&lt;2+&gt;为2个.所有配位氧都属于不同的P0_4四面体。因此，在该复合体上出现了不对称中心。一对对映体存在于一个晶胞中，因此晶体是外消旋的。目前正在进行进一步的工作来合成手性磷酸酯配合物。

Various structural materials of cyclohexaphosphate with metal ions and cations of organic amines were synthesized with the intention of exploring chiral solid catalysts for asymmetric organic syntheses. All the synthesized crystal materials were characterized structurally. The organic cations of aliphatic amines are very important for forming structures because the monomeric cyclohexaphosphate anions neutralized with the organic cations were linked together through hydrogen bondings between the organic cations, thus forming two-dimensional network in the structures. When metal canons are present in the system, the metal cations play a role to connect cyclohexaphosphate anions, and then a infinite chain of metal cation-cyclohexaphosphate is formed, of which positive change is neutralized with again the organic cations which allows the formation of three-dimensional networks.In the case of [Cu(bpy)_2] [Cu(bpy)] [Cu(bpy)(py)]P_6O_<18->10H_20, the structural analysis proved that the hexametaphosphaste complex was crystallized through a self-assembling with discrete molecules. Three different Cu^2^- existed by coordinating with oxygens of the hexametaphosphate anion in different manners. The number of coordinated oxygens is one for [Cu(bpy)_2]^<2+>, three for (Cu(bpy)]^<2+>, and two for [Cu(bpy)(py)]^<2+>. All the coordinated oxygens belong to different P0_4 tetrahedra each other. Therefore an asymmetric center appeared on this complex. A pair of those enantiomer existed in an unit cell, thus the crystal was racemate. Further works are undertaken now to synthesize chiral phosphate complexes.