Abstract
The synthesis of novel ruthenium(II) meso-tetra-(benzo-15-crown-5)-porphyrinates, meso-[( B 15 C 5)4 Por ] Ru ( CO )( MeOH ) (1) and meso-[( B 15 C 5)4 Por ] Ru ( L )2 (2)-(4) (meso-[( B 15 C 5)4 Por ]2-= 5,10,15,20-tetrakis-(benzo-15-crown-5)-porphyrinato-dianion; L = pyridine (py), pyrazine (pyz), 4,4′-bipyridyl (4,4′-bpy)), where CO and MeOH , or two N -donor ligands are axially coordinated to the central metal, are reported. The metalation of the free ligand performed by the reaction of Ru 3( CO )12 with meso-[( B 15 C 5)4 Por ] H 2 in 1,2,4-trichlorobenzene (TCB, bp = 215°C), gives (1) in a high yield. The synthesis of (2)-(4) involves the decarbonylation of (1) with trimethylamine N -oxide (( CH 3)3 NO ) in the presence of an excess of the N -donor ligand. The coordination of the axially bonded ligands is evidenced by different spectroscopic data.
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