N-错位卟啉锰、铁和钴配合物的合成及其应用

Synthesis of N-confused Porphyrin Manganese,Iron and Cobalt Complexes and Their Applications

N-错位卟啉锰、铁和钴配合物的合成与应用研究已成为当今卟啉化学的前沿课题之一.本文综述了N-错位卟啉锰、铁和钴配合物的合成及其在催化化学和生物化学等领域的研究进展,系统介绍了N-错位卟啉锰、铁和钴配合物的合成及其在催化烯烃氧化、环丙烷化、亚硝酸根还原酶和化学核酸酶等领域的应用.

Study on the synthesis and applications of N-confused porphyrin manganese,iron and cobalt complexes has be-come one of the hot topics of porphyrin chemistry.Compared with the coordination chemistry of porphyrin,that of N-confused porphyrin is complicated because of the peripheral nitrogen atom,the intramolecular C—H bond and NH tau-tomerism.N-confused porphyrin has two NH tautomers,isomer A and isomer B.Varied functions are observed in the coordi-nation chemistry of N-confused porphyrin such as stabilization of unusual metal oxidation states and metal-carbon bond for-mation.N-confused porphyrins have flexible character toward the metal oxidation state.Removal of the number of hydrogen atoms from one to three will result in a monanionic,dianionic and trianionic macrocycle.The various metal oxidation states are observed in N-confused porphyrin manganese,iron and cobalt complexes.The monovalent character of N-confused por-phyrin is observed in cobalt chemistry such as CoII(2-N-RNCTPP)Cl and CoII(NCTPP).The cobalt metal takes a valence of+2 since CoII(2-N-RNCTPP)Cl has a monoanionic axial ligand and N-confused porphyrin ligand.The squar-planar Co(Ⅱ)complex CoII(NCTPP)exists the cobalt-carbon bond.The divalent and trivalent characters of N-confused porphyrins are observed in manganese,iron and cobalt chemistry.In Mn(Ⅱ)and Fe(Ⅱ)complexes of N-confused porphyrin MnII(NHCTPP)Br and FeII(NHCTPP)Br,oxidation of the metal center is observed through intramolecular C—H bond activa-tion of N-confused porphyrin ligand,which can be converted into Mn(Ⅲ)and Fe(Ⅲ)complexes MnⅢ(NCTPP)Br and FeⅢ(NCTPP)Br on exposure to air in solutions.{FeNO}6 with a linear Fe-NO conformation is observed in the iron chemistry of N-confused porphyrin,which is unusually stable among the porphyrin iron nitrosyl complexes.It implies that iron N-confused porphyrin complexes can be used to study NO delivery and storage.This review covers the progress on the syn-thesis of N-confused porphyrin manganese,iron and cobalt complexes and their applications in the field of catalytic chemis-try and biological chemistry.The synthesis methods of N-confused porphyrin manganese,iron and cobalt complexes and their applications in catalytic oxidation,cyclopropanation of alkene,nitrate reductase activity and chemical nuclease activity are introduced systematically.