Synthesis, crystal structure and reactivity of trans-diaquo N,N'-ethylenebis-(3-methoxysalicylideneiminato)chromium(III)

Abstract

A new chromium(III) Schiff base complex, [Cr(3-methoxysalen)(H₂O)₂]ClO₄, where salen=N,N^r-ethylenebis-(salicylideneimine), has been synthesized and characterized by spectroscopic techniques. Single crystal X-ray data reveals that the complex assumes a trans-diaquo structure with formulation [Cr(C₁₈H₂₂>N₂O₆)]ClO₄ but, unlike in Cr (salen)(H₂O)₂ ⁺, the two trans-water molecules are equidistant from Cr^III. The effect of the substituent on the phenyl ring in respect of redox reactivity has been investigated. The kinetics of the oxidation of [Cr(Schiff base)- (H₂O)₂]ClO₄, where Schiff base=salen, (1) and 3-OMe-salen, (2) by PhOI has been studied. The bimolecular rate constant for the formation of the O=Cr^v Schiff base in case of (2) was four times faster than that of (1). The introduction of the OMe group substituent on the phenyl ring influences not only the structure and crystal packing, but also the reactivity of the complex and the electronic environment around the metal ion.