Iron Coordination Chemistry of Phenylpyruvate: An Unexpected kappa3-bridging mode that leads to oxidative cleavage of the C2-C3 bond.

One mononuclear iron(II)-phenylpyruvate complex [Tp(Ph2)Fe(II)(PPH)] (1) of the tridentate face-capping Tp(Ph2) ligand and two dinuclear iron(II)-phenylpyruvate enolate complexes [(6-Me3-TPA)2Fe(II)2(PP)]2+ (2) and [(6-Me3-TPA)2Fe(II)2(2-NO2-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 kappa2-(O,O) manner to the mononuclear Fe(II)(Tp(Ph2)) center of 1 but bridges in a kappa3-(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 Tp(Ph2) ligand. In contrast, dinuclear complexes 2 and 3 react with O2 to undergo oxidative cleavage of the C2-C3 bond of phenylpyruvate.