Synthesis and characterization of novel 99gTc(V) and Re(V) complexes with water-soluble tetraaza diamido dipyridino ligands: single-crystal X-ray structural investigations of mono- and dinuclear complexes.
Synthesis and characterization of novel 99gTc(V) and Re(V) complexes with water-soluble tetraaza diamido dipyridino ligands: single-crystal X-ray structural investigations of mono- and dinuclear complexes.
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具有水溶性四氮杂二酰胺二吡啶配体的新型 99gTc(V) 和 Re(V) 配合物的合成和表征：单核和双核配合物的单晶 X 射线结构研究。
DOI：
10.1021/ic020434q
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
Pandurangi,RaghoottamaS
中科院分区：
文献类型：
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作者：
Kurti,Laszlo;Papagiannopoulou,Dioni;Papadopoulos,Minas;Pirmettis,Ioannis;Raptopoulou,CatherineP;Terzis,Aris;Chiotellis,Efstratios;Harmata,Michael;Kuntz,RobertR;Pandurangi,RaghoottamaS
铼和锝以其在核医学中具有类似性质的有用应用而闻名。本研究合成了新的二氨基二吡啶（N4）水溶性配体（2- c5h4nch2nhco）2CH2,1(L1H2), (2- c5h4nnhnhco)2CH2,2和[2- c5h4n +(O)-CH2NHCO]2CH2,3。L1H2与ReOCl3(PPh3)2反应生成新型六配位铼(V)配合物，反式reo (L1)(OEt),4。用光谱方法对配合物进行了表征，x射线晶体学分析表明，铼分别与配体的4个氮原子、去质子化乙醇的2个氧原子和氧基的2个氧原子以扭曲的八面体形状配位。在溶液中，络合物4转化为一个新的络合物5，该络合物被证明是双核络合物μ-氧[ReO(L1)]2O。与[n-Bu4N][ReOCl4]反应生成中性络合物[trans-[ReO(L1)]Cl。同样，当配体1与[n-Bu4N][99gTcOCl4]反应时，形成中性的trans-[99TcO(L1)]Cl络合物7，溶解后转化为阳离子络合物8，trans-[99TcO(L1)(OH2)]+Cl-。8的单晶x射线结构表明，锝的配位球是一个扭曲的八面体，四个氮原子在等平面上，双键氧和配位水占据顶端位置。8进一步溶解形成双核μ-氧[TcO(L1)]2O,9。本研究表明，Tc和Re在相同配体上的x射线结构证明，除了几何结构上的相似性外，在二氨基二吡啶体系溶液中具有相似的金属核结构。
Rhenium and technetium are known for their useful applications in nuclear medicine with similar properties. In this study, new diamido dipyridino (N4) water-soluble ligands (2-C5H4NCH2NHCO)2CH2,1(L1H2), (2-C5H4NNHNHCO)2CH2,2, and [2-C5H4N+(O)-CH2NHCO]2CH2,3, were synthesized. Reaction of L1H2 with ReOCl3(PPh3)2resulted in the novel six-coordinated rhenium(V) complex,trans-ReO(L1)(OEt),4. The complex was characterized by spectroscopic methods, and its X-ray crystallographic analysis revealed that rhenium is coordinated to four nitrogen atoms of the ligand and to two oxygen atoms from the deprotonated ethanol and the oxo group respectively in a distorted octahedral geometry. In solution, complex4was transformed to a new complex5, which was proved to be the dinuclear complex μ-oxo [ReO(L1)]2O. Reaction of1with [n-Bu4N][ReOCl4] resulted in the neutral complex6,trans-[ReO(L1)]Cl. Similarly, when ligand1was reacted with [n-Bu4N][99gTcOCl4], the neutraltrans-[99TcO(L1)]Cl complex7was formed, which upon dissolution transformed into a cationic complex8,trans-[99TcO(L1)(OH2)]+Cl-. The single-crystal X-ray structure of8reveals that the coordination sphere about technetium is a distorted octahedron with four nitrogen atoms in the equitorial plane, while doubly bonded oxygen and coordinated water occupy the apical positions. Further dissolution of8resulted in the formation of dinuclear μ-oxo [TcO(L1)]2O,9. This study shows that Tc and Re have similar metal core structures in solution for diamido dipyridino systems, besides similarity in geometrical structure, proved by the X-ray structures on the same ligands.