Bipodal Acylthiourea Ligands as Building Blocks for Bi-, Tetra-, and Polynuclear Oxorhenium(V) Complexes

Reactions of (NBu4)[ReOCl4] and 3,3,3′,3′-tetraalkyl-1,1′-isophthaloylbis(thioureas), H2phth(R2tu)2 where R = Et, i-Bu, in hot MeOH with the addition of Et3N give red products of the composition [ReO(OMe){phth(R2tu)2}]2 (8a, R = Et; 8b, R = i-Bu). X-ray structures of 8 reveal symmetric binuclear complexes containing two almost coplanar organic ligands, each of which coordinates to two rhenium centers via the two bidentate-O,S moieties. The octahedral coordination spheres of the rhenium atoms are completed by each one oxo and one methoxido ligand which are directed perpendicular to the plane defined by the {phth(R2tu)2}2− ligands. While in 8a, both methoxido ligands point to the same side of the described plane and form a syn isomer, the MeO− ligands in 8b are located at opposite sides and form an anti isomer. Studies in solution show that there exists a reversible equilibrium between the anti and syn isomers. Dimerization/condensation of complexes 8 with the formation of tetranuclear complexes of the composition [{ReO{phth(R2tu)2}}2O]2 (9) and/or polynuclear species is observed in solutions, which do not contain MeOH.