Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility.

Iron and manganese complexes with derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine (bispicen) have previously been found to be efficient catalysts for hydrocarbon oxygenation. Methylation can potentially impact the conformation of the ligand around the metal center and the electronic character of the bound metal ion; each of these, in turn, impacts reactivity. Reported are mononuclear manganese(II) and iron(II) compounds with bispicen and five increasingly methylated derivatives. The extent and sites of methylation strongly impact the optical and electrochemical properties of the manganese and iron complexes. Increased methylation is correlated with more positive M(III/II) reduction potentials. Structural analysis of the Mn(II) series reveals two ligand conformations that have never been observed for the bispicen framework, cis-β and trans, in addition to the common cis-α conformation. (1)H NMR spectra of the structurally characterized iron compounds are consistent with mixtures of these conformers, suggesting that bispicen coordination is both more flexible and more dynamic than previously thought.