Rhodium(III) Azuliporphyrins

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• 作者：Leah M. Stateman ; Gregory M. Ferrence ; Timothy D. Lash
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 10, 2015
• 年：2015
• 卷：34
• 期：15
• 页码：3842-3848
• 全文大小：462K
• ISSN：1520-6041

文摘

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鈥?7% yield. These derivatives incorporate solvent molecules as axial ligands and thereby introduce two carbon鈥搑hodium bonds in a three-component reaction. The methylbenzyl ligands that are derived from xylenes overlie the 蟺 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.