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Generation of trans-dioxoruthenium(VI) porphyrins: A photochemical approach |
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| Authors: | Rui Zhang |
| Institution: | Department of Chemistry, Western Kentucky University, Bowling Green, KY 42101-1079, USA |
| Abstract: | trans-Dioxoruthenium(VI) porphyrin complexes have been developed as one of the best-characterized model systems for heme-containing enzymes. Traditionally, this type of compounds can be prepared by oxidation of ruthenium(II) precursors with peroxyacids and other terminal oxidants under different conditions, depending on the porphyrin ligands. In this work, a new photochemical generation of trans-dioxoruthenium(VI) porphyrins has been developed by extension of the known photo-induced ligand cleavage reactions. Refluxing ruthenium(II) carbonyl porphyrins RuII(Por)(CO)] in carbon tetrachloride afforded dichlororuthenium(IV) complexes RuIV(Por)Cl2]. Facile exchange of the counterions in RuIV(Por)Cl2] with Ag(ClO3) or Ag(BrO3) gave the corresponding dichlorate RuIV(Por)(ClO3)2] or dibromate RuIV(Por)(BrO3)2] salts. Visible-light photolysis of the photo-labile porphyrin-ruthenium(IV) dichlorates or dibromates resulted in homolytic cleavage of the two O-Cl or O-Br bonds in the axial ligands to produce trans-dioxoruthenium(IV) species RuVI(Por)O2] bearing different porphyrin ligands. |
| Keywords: | Por porphyrin TMP 5 10 15 20-tetramesitylporphyrin dianion D4-Por&lowast 5 10 15 20-tetrakis[(1S 4R 5R 8S)-1 2 3 4 5 6 7 8-octahydro-1 4:5 8dimethanoanthracen-9-yl]porphyrin dianion TPP 5 10 15 20-tetraphenylporphyrin dianion 4-MeO-TPP 5 10 15 20-tetra(4-methoxyphenyl)porphyrin dianion 4-CF3-TPP 5 10 15 20-tetra(4-trifuoromethylphenyl)porphyrin dianion TPFPP 5 10 15 20-tetrapentafluorophenylporphyrin dianion m-CPBA meta-chloroperoxybenzoic acid |
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