A family of oxorhenium(v) complexes incorporating chelated monoanionic ONN reduced Schiff base and dianionic ONNO tetradentate ligands: synthesis, spectroscopic and electrochemical studies.

The green colored complexes of the type Re(V)O(L(SB))Cl(2), 1, have been synthesised by reacting NBu(4)[ReOCl(4)] with HL(SB) in dry ethanol. Here, L(SB)(-) are the deprotonated forms of N-(2-hydroxybenzyl)-2-picolylamine (HL(SB)(1)); N-(2-hydroxybenzyl)-N',N'-dimethylethylenediamine (HL(SB)(2)) and N-(2-hydroxybenzyl)-N',N'-diethylethylenediamine (HL(SB)(3)). Similarly, NBu(4)[ReOCl(4)] reacted with N,N-bis(2-hydroxybenzyl)-2-picolylamine (H(2)L(1)); N,N-bis(2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H(2)L(2)); N,N-bis(2-hydroxybenzyl)-N',N'-diethylethylenediamine (H(2)L(3)); [N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)]-2-aminoethanol (H(2)L(4)); [N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)]-2-methyl-2-amino-1-propanol (H(2)L(5)); N,N-bis(1-hydroxyethyl)-2-picolylamine (H(2)L(6)), to give the monochloro complexes Re(V)O(L)Cl, 2. The X-ray structures of the complexes are reported. The molecular structures observed in the solid state are preserved in solution ((1)H NMR). In acetonitrile solution the Re(V)O(L)Cl, 2, display a one-electron couple, Re(VI)O(L)Cl(+)-Re(V)O(L)Cl, near 1.0 V vs SCE. The electrogenerated hexavalent complexes [Re(VI)O(L)Cl]ClO(4), 3, are paramagnetic and display sextet EPR spectra in solution at room temperature (A(av) approximately 417 (G), g approximately 1.914).