化学模拟生物固氮——Ⅸ 铁钼辅基模型化合物的合成和性能表征

Abstract

[中文文摘]采用乙二醇基阴离子作为活插头(可通过水解除去的双配位螯形配位体),对前文提出的合成方法作了重要改进,以期所合成的铁钼辅基模型化合物中Mo~(Ⅳ(Ⅲ))第一配位界内两个不稳定的配位体处于相邻的位置,如厦门模型Ⅲ(或厦门模型Ⅱ)所要求。合成和重组活性评价结果,重组活性比使用乙腈等为活插头的提高2个数量级,化学催化活性和选择性接近于天然FeMo-co水平。[英文文摘]A significant improvement has been made to the method previously proposed[3] for synthesizing FeMo-co modeling compounds. With the use of ethylene glycolate anion as labilizable blocking agent (hydrolyzable bidentatc chelating ligand)to protect two neighboring coordination sites in the first coordination sphere of MoIV(III) of the synthesized FeMo-co modeling compound, an increase in reconstituted-nitrogenase activity of 2 orders of magnitude of the sample synthesized (as compared with the use of acetoni-trile or other monodentare ligands as bloeking agents)has been obtained.Catalytic activity and selectivity assays as well as preliminary characterization by EPR method have also been made.