On the Structure and Reactivity of Peroxotransition-Metal Complexes.

Abstract

The electronic structures of an early and a late h2-peroxotransition-metal complex have been investigated in an attempt to account for the similarities in the M-O and O-O bond lengths and the differences in reactivity in spite of the structural similarities around the metal peroxo group. Peroxotitanium(IV) 2,6-pyridinedicarboxylate is used as a model for an early h2-peroxotransition-metal complex while the late h2-peroxotransition-metal complex is modelled by peroxonickel(II) bis (t-butylisocyanate). The h2-peroxotitanium complex is most stable in the 1A1 state and the h2-peroxonickel complex in the 3B2 state. The bonding between the metal atom and the peroxo fragments is analyzed both in terms of the frontier orbitals and orbital population anal. The reactivity of the two complexes with org. substrates is briefly discussed. [on SciFinder (R)]