Non-Heme FeII Diastereomeric Complexes Bearing a Hexadentate Ligand: Unexpected Consequences for the Spin State and Catalytic Oxidation Properties.

Abstract

The reactivity and selectivity of non-heme FeII complexes as oxidation catalysts can be substantially modified by alteration of the ligand backbone or introduction of various substituents. In comparison with the hexadentate ligand N,N,N',N'-tetrakis(pyridin-2-ylmethyl)ethane-1,2-diamine (TPEN), N,N'-bis[1-(pyridin-2-yl)ethyl]-N,N'-bis(pyridin-2-ylmethyl)ethane-1,2-diamine (2Me L6 2 ) has a methyl group on two of the four picolyl positions. FeII complexation by 2Me L6 2 yields two diastereomeric complexes with very similar structures, which only differ in the axial/equatorial positions occupied by the methylated pyridyl groups. In solution, these two isomers exhibit different magnetic behaviors. Whereas one isomer exhibits temperature-dependent spin-state conversion between the S=0 and S=2 states, the other is more reluctant towards this spin-state equilibrium and is essentially diamagnetic at room temperature. Their catalytic properties for the oxidation of anisole by H2 O2 are very different and correlate with their magnetic properties, which reflect their lability/inertness. These different properties most likely depend on the different steric constraints of the methylated pyridyl groups in the two complexes.