Schiff base chemistry of the {ReO} core: structural characterization of the unusual '3 + 2' complex [ReO(eta-OC(6)H(4)-CH=NC(6)H(4)-2-S)(eta-OC(6)H(4))].

The reaction of [ReOCl(3)(PPh(3))(2)] with salicylaldehyde-2-mercaptoanil (1) in methanol yields [ReO(OCH(3))(PPh(3))(eta(3)-OC(6)H(4)CH=NC(6)H(4)S)] (3). Reaction of 3 with 2-(2-hydroxyphenyl)benzothiazole (2) produces [ReO(eta(3)-OC(6)H(4)CH=NC(6)H(4)S)( eta(2)-OC(6)H(4))] (4) in good yield. Compound 4 may also be prepared directly from the reaction of [ReOCl(3)(PPh(3))(2)] with excess 1, after prolonged reaction times in the presence of atmospheric oxygen. The structure of 3 exhibits a distorted octahedral Re(V) center coordinated to a terminal oxo-group, a methoxy ligand, a triphenylphosphine ligand, and the N, O and S donors of the tridentate Schiff base ligand. The octahedral geometry of 4 is defined by the terminal oxo-group, the N, O and S donors of the tridentate Schiff base ligand, and the N and O donors of the bidentate 2-(2-hydroxophenyl)benzothiazole ligand. Oxidation and cyclization of the Schiff base salicylaldehyde-2-mercaptoanil to produce 2-(2-hydroxyphenyl)benzothiazole is precedented and in this instance may be driven by the formation of the robust '3+2' complex 4.