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

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• 作者：Hung Huy Nguyen ; Pham Chien Thang ; Axel Rodenstein ; Reinhard Kirmse ; Ulrich Abram
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：January 17, 2011
• 年：2011
• 卷：50
• 期：2
• 页码：590-596
• 全文大小：918K
• 年卷期：v.50,no.2(January 17, 2011)
• ISSN：1520-510X

文摘

Reactions of (NBu₄)[ReOCl₄] and 3,3,3鈥?3鈥?tetraalkyl-1,1鈥?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鈭?/sup> ligands. While in 8a, both methoxido ligands point to the same side of the described plane and form a syn isomer, the MeO鈭?/sup> 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.}