Synthesis, crystal structure of two new Zn(II), Cu(II) porphyrins and their catalytic activities to ethylbenzene oxidation

• One novel metal free and two metal porphyrins were synthesized and characterized.
• Two single crystal structures of Cu(II) and Zn(II) porphyrin were analyzed.
• Catalytic activities of metalloporphyrins to ethylbenzene oxidation were examined.

One novel porphyrin 5,10,15,20-tetra(4-(4-acetateethyl)phenoxy)phenylporphyrin (H2Pp), and its two corresponding zinc(II) and copper(II) porphyrins (ZnPp, CuPp) is synthesized and characterized by spectroscopic techniques. The single crystal structures of [ZnPp(DMF)]·DMF (1) and [CuPp(DMF)] (2) are also obtained and analyzed. Complex 1 crystallizes in monoclinic system compared to the triclinic system of complex 2, which may due to the influence of solvent DMF molecule in 1. The metal centers have similar coordination environments in the two structures, which are all five-coordinated pyramid geometry with four nitrogen atoms of porphyrin ring from equator and an axial oxygen atom of DMF molecule. 1 and 2 display 3D supramolecular structures constructed by π⋯π interactions of porphyrin rings and C–H⋯O hydrogen bonds. The catalytic activities of 1 and 2 to the ethylbenzene oxidation are examined. The results indicate that both of them exhibit highly selectivity to acetophenone (> 99%) with the conversion of 23% (1) and 76% (2) respectively.

Two novel supramolecular structures of zinc(II), copper(II) porphyrins were analyzed, and copper(II) porphyrin showed high catalytic activities to the ethylbenzene oxidation.Figure optionsDownload as PowerPoint slide