Synthesis and Electrochemical Characterization of Ruthenium Porhyrins containing a Bound PF3 Axial Ligand

Article abstract of DOI:10.1039/DT9930001167

The first synthesis and electrochemistry of metalloporphyrins containing a bound PF3 axial ligand has been achieved.The investigated compounds are where por is the dianion of 5,10,15,20-tetraphenyl-, -tetra(p-bromophenyl)-, -tetra(p-methoxyphenyl)-, 2,7,12,17-tetraethyl-3,8,13,18-tetramethyl- or 2,3,7,8,12,13,17,18-octaethyl-porphyrin.Each species was investigated with respect to its spectroscopic and electrochemical properties and the resulting data compared with those for having the same porphyrin ring.A number of similarities exist between the carbonyl and PF3 derivatives in methylene chloride but major differences can be observed in other non-aqueous solutions.The first reduction of each complex is reversible in tetrahydrofuran (thf) and leads to a porphyrin ?-anion radical rather than a ruthenium(I) species as identified by UV/VIS spectroelectrochemistry.Each investigated complex also undergoes two reversible oxidations in dichloromethane, the first of which leads to a porphyrin ?-cation radical.The derivatives appear to be more stable than the analogues in thf or CH2Cl2, but an electrochemically initiated conversion of II(por)(PF3)(py)> into III(Por)(py)2>(1+) can be readily accomplished in pyridine (py) or CH2Cl2-pyridine mixtures.This type of reaction has never been seen upon oxidation of a ruthenium(II) porphyrin and was monitored by cyclic voltammetry and UV/VIS spectroelectrochemistry.

Full text of DOI:10.1039/DT9930001167

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