2座配位性ポルフィリンの有機金属錯体

概要

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The N21, N22-etheno-bridged porphyrin was used as a bidentate nitrogen ligand applicable to organometallic chemistry. X-ray crystallography of Rh and Pd complexes of the bidentate porphyrin ligand indicated that a N-M-N plane is canted by 53 63° from the mean porphyrin plane. The metal complexes of this bidentate porphyrin are stable not only against the elimination of the N21, N22- bridge, but also against the ligand substitution by strongly coordinating ligands such as ethylenediamine and isocyanide. Some organopalladium porphyrins were synthesized and their properties were investigated. Apparent ligand rotation in the (π-allyl) Pd porphyrin occurred by way of the dissociation of a Pd-N bond and the activation free energy was much larger than those measured for the corresponding phenanthroline Pd complexes. Insertion of CO, isocyanide, and alkenes into the Pd-C bond of (methyl) Pd porphyrins proceeded in good yields. The stereochemical features of these organopalladium porphyrins were determined by NMR with the aid of the porphyrin ring current effect. Stereochemical and electronic interaction of the organo ligand with the bidentate porphyrin ligand were observed.
社団法人有機合成化学協会の論文
2004-12-01