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

作者：Hung Huy Nguyen^*; Pham Chien Thang; Rodenstein Axel; Kirmse Reinhard; Abram Ulrich

来源：Inorganic Chemistry, 2011, 50(2): 590-596.

DOI：10.1021/ic1017642

Reactions of (NBu4)[ReOCl4] and 3,3,3',3'-tetraalkyl-1,1'-isophthaloylbis(thioureas), H(2)phth(R(2)tu)(2) where R = Et, i-Bu, in hot WON wit h the addition of Et3N give red products of the composition [ReO(OMe){phth(R(2)tu)(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(R(2)tu)(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(R(2)tu)(2)}}(2)O](2) (9) and/or polynuclear species is observed in solutions, which do not contain MeOH.

• 出版日期2011-1-17