Bis(acetylacetonato)bis(pyrazolato)ruthenate(iii) as a redox-active scorpionate ligand.

Abstract

The potential of a new anionic octahedral metal complex [Ru(III)(acac)2(pz)2](-) ((-)) (pzH = pyrazole) as a ligand with a scorpionate coordination behaviour like tris(pyrazolyl)borate (tp) and reversible redox activity is presented. Trinuclear metal complexes, [Ru(III)2Zn(II)(acac)4(pz)4] () and [Ru(II)Ru(III)2(acac)4(pz)4] (), were each synthesized by the reaction of ZnCl2 or Ru3(CO)12 with [Ru(III)(acac)2(pz)(pzH)] (H) that is in situ deprotonated and acts as a precursor of (-). Single-crystal X-ray diffraction studies clarified that (-) acts as a scorpionate ligand; two (-) units in and one unit in function as bidentate ligands with two pyrazolates as pincers, while another (-) unit in functions as a tridentate ligand with one oxygen atom as a tail in addition to the two pyrazolate pincers. Moreover, and showed reversible multi-stage redox behaviours based on the Ru(II)/Ru(III) and Ru(III)/Ru(IV) couples of the (-) units in the cyclic voltammetry (CV) measurements. Based on the X-ray, IR, and CV measurements and the comparison with other Ru(ii) complexes with tp derivatives, the (-) unit was found to act as a redox-active scorpionate with electron withdrawing properties compared to the tp.