Aqua-complexes of pyrimidine-4,6-dicarboxylic acid and its monoester with organometallic fac-[M(CO)3]+ (M = Re and 99mTc) core as radiopharmaceutical probes: Synthesis and characterization
{"title":"Aqua-complexes of pyrimidine-4,6-dicarboxylic acid and its monoester with organometallic fac-[M(CO)3]+ (M = Re and 99mTc) core as radiopharmaceutical probes: Synthesis and characterization","authors":"","doi":"10.1016/j.jorganchem.2024.123348","DOIUrl":null,"url":null,"abstract":"<div><p>The current study highlights on the synthesis and characterization of aqua-complexes of the <em>fac</em>-[M(CO)<sub>3</sub>]<sup>+</sup> (M = Re and <sup>99m</sup>Tc) core with pyrimidine-4,6-dicarboxylic acid (H<sub>2</sub>pmdc) and its monoester 6-(ethoxycarbonyl)pyrimidine-4-carboxylic acid (Hetpmdc), which are the model for future design of imaging and therapeutic radiopharmaceuticals. Complexes [M(CO)<sub>3</sub>(OH<sub>2</sub>)(Hpmdc)] (M = Re (<strong>1</strong>) and <sup>99m</sup>Tc (<strong>2</strong>)) were formed from the reaction of H<sub>2</sub>pmdc with [Re(CO)<sub>5</sub>Br] in water and aqueous solution of [<sup>99m</sup>Tc(CO)<sub>3</sub>(OH<sub>2</sub>)<sub>3</sub>]<sup>+</sup> respectively. The reaction of [<em>Re</em>(CO)<sub>5</sub>Br] with H<sub>2</sub>pmdc in ethanol (EtOH) has also studied and led to the complex [Re(CO)<sub>3</sub>(OH<sub>2</sub>)(etpmdc)] (<strong>3</strong>), where etpmdc<sup>−</sup>is 6-(ethoxycarbonyl)pyrimidine-4-carboxylate anion which was formed from the mono-esterification of H<sub>2</sub>pmdc in parallel with its coordination to the <em>fac</em>-[Re(CO)<sub>3</sub>]<sup>+</sup> unit. The complex [<sup>99m</sup>Tc(CO)<sub>3</sub>(OH<sub>2</sub>)(etpmdc)] (<strong>4</strong>) was formed in parallel with <strong>2</strong> by reacting H<sub>2</sub>pmdc with aqueous solution of [<sup>99m</sup>Tc(CO)<sub>3</sub>(OH<sub>2</sub>)<sub>3</sub>]<sup>+</sup> and ethanol. The chemical identification of <strong>1</strong> and <strong>3</strong> was achieved by using <sup>1</sup>H NMR, <sup>13</sup>C NMR, IR, ESI-MS and elemental analysis. Complex <strong>3</strong> was furtherly identified by using single crystal X-ray crystallography. The structural similarities of <strong>1</strong> and <strong>2</strong> was assessed by coinjection of both complexes in the HPLC with UV/Vis detection coupled with a γ-detector followed by comparison of retention times of the γ-peak of <strong>2</strong> and the UV-peak of <strong>1</strong> which allowed unambiguous identification of <strong>2</strong>. Similarly, the formation of complex [<sup>99m</sup>Tc(CO)<sub>3</sub>(OH<sub>2</sub>)(etpmdc)] (<strong>4</strong>) in parallel with <strong>2</strong> was assessed by coinjection of complexes <strong>1</strong> and <strong>3</strong> with the product from the reaction of H<sub>2</sub>pmdc with aqueous solution of [<sup>99m</sup>Tc(CO)<sub>3</sub>(OH<sub>2</sub>)<sub>3</sub>]<sup>+</sup> and ethanol in the same HPLC as one used for the structural identification of <strong>2</strong> followed by comparison of retention times of the γ-peaks of <strong>2</strong> and <strong>4</strong> and the UV-peaks of <strong>1</strong> and <strong>3</strong>.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X24003437","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The current study highlights on the synthesis and characterization of aqua-complexes of the fac-[M(CO)3]+ (M = Re and 99mTc) core with pyrimidine-4,6-dicarboxylic acid (H2pmdc) and its monoester 6-(ethoxycarbonyl)pyrimidine-4-carboxylic acid (Hetpmdc), which are the model for future design of imaging and therapeutic radiopharmaceuticals. Complexes [M(CO)3(OH2)(Hpmdc)] (M = Re (1) and 99mTc (2)) were formed from the reaction of H2pmdc with [Re(CO)5Br] in water and aqueous solution of [99mTc(CO)3(OH2)3]+ respectively. The reaction of [Re(CO)5Br] with H2pmdc in ethanol (EtOH) has also studied and led to the complex [Re(CO)3(OH2)(etpmdc)] (3), where etpmdc−is 6-(ethoxycarbonyl)pyrimidine-4-carboxylate anion which was formed from the mono-esterification of H2pmdc in parallel with its coordination to the fac-[Re(CO)3]+ unit. The complex [99mTc(CO)3(OH2)(etpmdc)] (4) was formed in parallel with 2 by reacting H2pmdc with aqueous solution of [99mTc(CO)3(OH2)3]+ and ethanol. The chemical identification of 1 and 3 was achieved by using 1H NMR, 13C NMR, IR, ESI-MS and elemental analysis. Complex 3 was furtherly identified by using single crystal X-ray crystallography. The structural similarities of 1 and 2 was assessed by coinjection of both complexes in the HPLC with UV/Vis detection coupled with a γ-detector followed by comparison of retention times of the γ-peak of 2 and the UV-peak of 1 which allowed unambiguous identification of 2. Similarly, the formation of complex [99mTc(CO)3(OH2)(etpmdc)] (4) in parallel with 2 was assessed by coinjection of complexes 1 and 3 with the product from the reaction of H2pmdc with aqueous solution of [99mTc(CO)3(OH2)3]+ and ethanol in the same HPLC as one used for the structural identification of 2 followed by comparison of retention times of the γ-peaks of 2 and 4 and the UV-peaks of 1 and 3.
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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