Iron coordination chemistry of phenylpyruvate: An unexpected κ3-bridging mode that leads to oxidative cleavage of the C2-C3 Bond

Tapan K. Paine, Hui Zheng, Lawrence Que

Research output: Contribution to journalArticle

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Abstract

One mononuclear iron(II)-phenylpyruvate complex [TpPh2Fe II(PPH)] (1) of the tridentate face-capping TpPh2 ligand and two dinuclear iron(II)-phenylpyruvate enolate complexes [(6-Me 3-TPA)2FeII2(PP)]2+ (2) and [(6-Me3-TPA)2FeII2(2-NO 2-PP)]2+ (3) of the tetradentate 6-Me3-TPA ligand are reported to demonstrate two different binding modes of phenylpyruvate to the iron(II) centers. Phenylpyruvate binds in a κ2-(O,O) manner to the mononuclear FeII(TpPh2) center of 1 but bridges in a κ3-(O,O,O) fashion to the two Fe II(6-Me3-TPA) centers of 2 and 3. Mononuclear complex 1 reacts with O2 to undergo oxidative decarboxylation and ortho-hydroxylation of one of the aromatic rings of the TpPh2 ligand. In contrast, dinuclear complexes 2 and 3 react with O2 to undergo oxidative cleavage of the C2-C3 bond of phenylpyruvate.

Original languageEnglish (US)
Pages (from-to)474-476
Number of pages3
JournalInorganic chemistry
Volume44
Issue number3
DOIs
StatePublished - Feb 7 2005

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