Rhenium Complexes Based on an N₂O Tridentate Click Scaffold: From Synthesis, Structural and Theoretical Characterization to a Radiolabelling Study

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• 作者：Romain Eychenne ; Sihem Guizani ; Jin-Hui Wang ; Claude Picard ; Nadia Malek ; Paul-Louis Fabre ; Mariusz Wolff ; Barbara Machura ; Nathalie Saffon ; Nicolas Lepareur and Eric Benoist
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2017
• 出版时间：January 3, 2017
• 年：2017
• 卷：2017
• 期：1
• 页码：69-81
• 全文大小：2097K
• ISSN：1099-0682c

文摘

A general synthetic approach to a novel range of semirigid bifunctional chelating agents (BCAs) that include an aromatic ring and a triazolyl moiety in the chelating unit has been investigated for the fac-[M(CO)₃]⁺ core (M = ^185/187Re or ¹⁸⁸Re). The strategy includes the facile preparation of these N₂O ligands bearing various functionalized arms (carboxylate, terminal alkyne, aromatic amine). The reaction of commercial [Re(CO)₅Cl] {or a freshly prepared [Re(OH₂)₃(CO)₃]⁺ precursor} with our BCAs in methanol led to the formation of stable neutral tricarbonylrhenium complexes of general formula [Re(CO)₃(L)] (LH = 5, 10, 11) in high yields. These compounds were characterized by IR and NMR spectroscopy, mass spectrometry, electrochemistry, and X-ray crystallography for [Re(CO)₃(5_–H)] and [Re(CO)₃(11_–H)] as well as by DFT calculations. The analogous rhenium-188 complexes [¹⁸⁸Re(CO)₃(5)] and [¹⁸⁸Re(CO)₃(11_–H)] were also prepared, in acceptable to excellent yields, by the reaction of 5 or 11 with the fac-[¹⁸⁸Re(OH₂)₃(CO)₃]⁺ precursor in methanol at 80 °C. The structural identities of the radioactive complexes were assessed by HPLC studies. The good affinity of these click ligands for the Re^I core combined with the ease of their derivatization make this chelating system promising for the conception of target-specific radiopharmaceuticals for therapeutic purposes.