Metal-metal bonds extended over a porphyrin ring

Abstract

Abstract Two new series of metal—metal bonded indium porphyrin complexes, (TBPP)In—ML and (5FP)In—ML, where TBPP is the dianion of 5,10,15,20-tetrakis (3,5-di-t-butylphenyl)porphyrin and 5FP is the dianion of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin, ML is Mn(CO)5, Mo(CO)3Cp, and Co(CO)4, have been synthesized in addition to (OEP)In—ML and (TPP)In—ML. These new metal—metal bonded porphyrin complexes have shown higher solubilities to organic solvents or higher photochemical stabilities as compared with (OEP)In—ML and/or (TPP)In—ML. (P)In—Co(CO)4 complexes where P denotes all of these porphyrin ligands have been obtained in almost quantitative yield by the reaction of (P)In—Cl with LiCo3(CO)10. These porphyrin complexes have shown typical UV-vis spectra to the hyper class. Analysis of the absorption spectra has revealed an anomalous character of (5FP)In—ML complexes. 17O and 13C NMR chemical shifts for CO ligands in (P)In—ML complexes have exhibited only small changes with the change of the porphyrin ligand for the same ML. IR data of (P)In—ML complexes in the ν(CO) region have clearly shown higher frequency shifts in inverse proportion to σ-donor ability of these four porphyrin ligands.