Synthesis and characterization of rhenium and Technetium-99 m tricarbonyl and dicarbonyl complexes with quinaldic acid and Arsenic/Phosphorus derivatives

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2024-09-22 DOI:10.1016/j.poly.2024.117236

Charalampos Triantis , Antonio Shegani , Aristeidis Chiotellis , Catherine Raptopoulou , Vassilis Psycharis , Maria Pelecanou , Ioannis Pirmettis , Minas Papadopoulos

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Abstract

The synthesis and characterization of neutral tricarbonyl fac-[Re/^99mTc(quin)(X)(CO)₃] and dicarbonyl cis–trans-[Re/^99mTc(quin)(X)₂(CO)₂] mixed ligand complexes with quinaldic acid (quin) as the bidentate ligand and trimethoxyphosphine [P(OCH₃)₃], tris(hydroxymethyl)-phosphine [P(CH₂OH)₃]_, triphenylphosphine (PPh₃), and triphenylarsine (AsPh₃) as the monodentate ligands (X) is described. The synthesis of the [2 + 1] tricarbonyl complexes proceeds by displacement of the water molecule of the fac-[Re/^99mTc(quin)(H₂O)(CO)₃] by the monodentate ligand. Interestingly, the synthesis of the [2 + 1 + 1] dicarbonyl complexes was achieved only for PPh₃ after replacing the CO group trans to PPh₃ with a second PPh₃ molecule. The latter complex was also obtained by refluxing quinaldic acid with the trans-mer-[Re(PPh₃)₂(Cl)(CO)₃] precursor in toluene. Rhenium complexes were prepared in satisfactory yields and fully characterized. At the technetium-99 m level, complexes were produced in high radiochemical yields and characterized by comparative chromatographic analysis using the analogous rhenium complexes. Complexes have shown varying stability against transchelation by cysteine and histidine in agreement with the decreasing σ-donating capacity of the monodentate ligand (P(OCH₃)₃ > P(CH₂OH)₃ > PPh₃ > AsPh₃. The stable complexes with PPh₃ showed high lipophilicity (LogP 2.90 and 3.10, respectively) due to the lipophilic nature of the monodentate ligands. The σ-donor and π-acceptor capacity of the monodentate ligand strongly influences the formation and stability of the complexes, and these characteristics should be considered before choosing the appropriate ligand for radiopharmaceuticals design.

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铼和锝-99 m 三羰基和二羰基与喹啉二酸和砷/磷衍生物配合物的合成与表征

中性三羰基面-[Re/99mTc(quin)(X)(CO)3]和二羰基顺反-[Re/99mTc(quin)(X)2(CO)2]混合配体配合物的合成与表征、三（羟甲基）膦 [P(CH2OH)3]、三苯基膦 (PPh3) 和三苯基胂 (AsPh3) 作为单齿配体 (X) 的混合配体配合物。通过单齿配体置换面-[Re/99mTc(quin)(H2O)(CO)3] 的水分子，合成 [2 + 1] 三羰基配合物。有趣的是，只有 PPh3 在用第二个 PPh3 分子取代反式到 PPh3 的 CO 基团后，才能合成 [2 + 1 + 1] 二羰基配合物。后一种配合物也是通过在甲苯中将喹啉二酸与反式-[Re(PPh3)2(Cl)(CO)3]前体回流得到的。铼配合物的制备收率令人满意，并已完全定性。在锝-99 m 级，络合物的放射化学收率很高，并通过使用类似的铼络合物进行色谱分析进行了表征。根据单齿配体（P(OCH3)3 > P(CH2OH)3 > PPh3 > AsPh3.由于单齿配体的亲油性，PPh3 的稳定配合物显示出较高的亲油性（LogP 分别为 2.90 和 3.10）。单齿配体的σ供体和π受体能力对配合物的形成和稳定性有很大影响，因此在选择合适的配体用于放射性药物设计之前应考虑这些特性。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.