Rhodium(III) Azuliporphyrins
收藏资源简介：
The organometallic chemistry of azuliporphyrins has been extended to the first syntheses of rhodium(III) derivatives. Reaction of [Rh(CO)2Cl]2 with an azuliporphyrin in refluxing xylenes gave rhodium(III) azuliporphyrins in 62–67% yield. These derivatives incorporate solvent molecules as axial ligands and thereby introduce two carbon–rhodium bonds in a three-component reaction. The methylbenzyl ligands that are derived from xylenes overlie the π system of the porphyrinoid macrocycle, and proton NMR spectra show that these units are strongly shielded. The o-, m-, and p-xylene-derived complexes were characterized by X-ray crystallography, and this confirmed the presence of the central rhodium atom and the axial benzylic ligands. Additionally, when the azuliporphyrin was reacted with [Rh(CO)2Cl]2 in refluxing acetonitrile and then treated with acetone and basic alumina, a rhodium(III) azuliporphyrin with an acetone-derived axial ligand was generated. These results demonstrate that azuliporphyrins are superior organometallic ligands and therefore merit further investigation.
