Design and creation of reaction active multinuclear metal complex

（1）磷酸三酯酶样水解功能双（μ-羧基）-μ-苯酚配合物[M_2（L）（AcO）_2]^+（M=Mn，Co，Ni，Zn）是一种基于“封端”型双核隔室配体的磷酸三酯酶模型化合物，催化三（对硝基苯基）磷酸酯（TNP）→二（对硝基苯基）磷酸酯（BNP^-）的水解。通过UV-vis和ESI质谱追踪水解。水解能力取决于双核的金属组合，其顺序为MnMn> ZnZn>CoCo>>NiNi。这一趋势很好地解释了水分子的亲核性结合的金属中心的顺序。实际磷酸三酯酶的活性中心不是MnMn，而是ZnZn双核，这是因为海水中Zn的天然丰度大于Mn。（2）类磷酸二酯酶水解功能用双核配合物[M_2（L）（AcO）_2]^+（M=Mn，Co，Ni，Zn）研究了双（对硝基苯基）磷酸酯（BNP^-）的水解。结果表明，水解反应是通过[M_2（L）（AcO）（BNP）]^+进行的，[M_2（L）（AcO）（BNP）]^+是由[M_2（L）（AcO）（BNP）]^++AcO^-= [M_2（L）（AcO）（BNP）]^++AcO^-平衡生成的，其水解能力依次为MnMn> CoCo>> NiNi>>ZnZn。ZnZn化合物[Zn_2（L）（AcO）_2]^+的水解能力很低，因为它与BNP-形成“刚性”的μ-乙酰基-μ-BNP核结构，不便于将水分子带到ZnZn核上。在自然界中，磷酸二酯酶的活性中心不是CoCo，而是MnMn，因为海洋中Co的天然丰度远低于Mn。并成功制备了第一个具有FeZn核结构的紫色酸性磷酸酶功能模型。

(1)Phosphotriesterase-like hydrolytic functionBis(μ-carboxylato)-μ-phenolatocomplexes, [M_2(L)(AcO)_2]^+(M=Mn,Co,Ni,Zn), based on ‘end-off' type dinucleating compartment ligand have been prepared as phosphotriesterase-model compounds which catalyze the hydrolysis of tris(p-nitrophenyl)phosphate (TNP)→bis(p-nitrophenyl)phosphate (BNP^-). The hydrolysis was traced by means of UV-vis and ESI mass spectra. The ability of hydrolysis depends on the metal combination of dinuclear core and decreased in the order, MnMn〜ZnZn>CoCo>>NiNi. This tendency is well explained by the order of nucleophilicity of water molecules binding to the metal centers. Actual phosphotriesterase has not MnMn but ZnZn dinuclear core as active sites, because natural abundance of Zn in the sea is more than that of Mn.(2)Phosphodiesterase-like hydrolytic functionHydrolysis of bis(p-nitrophenyl) phosphate (BNP^-) has been studied by using of dinuclear complexes, [M_2(L)(AcO)_2]^+ (M=Mn,Co,Ni,Zn). It was revealed that the hydrolysis progresses via [M_2(L)(AcO)(BNP)]^+ which was generated from an equilibrium [M_2(L)(AcO)_2]^++BNP^-= [M_2(L)(AcO)(BNP)]^++AcO^- and the ability of hydrolysis decreased in the order, MnMn〜CoCo>>NiNi>>ZnZn. The hydrolysis ability of ZnZn compound, [Zn_2(L)(AcO)_2]^+, is very low, because it forms ‘rigid' μ-acetato-μ-BNP core structure with BNP-, which is inconvenient to take water molecules on ZnZn core. In natural, phosphodiesterase has not CoCo but MnMn core as active sites, because natural abundance of Co in the sea is much less than that of Mn. Furthermore, the first function-model of purple acid phophatase which has FeZn core structure has been prepared successfully.