Papachristou Maria, Pirmettis Ioannis C, Tsoukalas Charalambos, Papagiannopoulou Dionyssia, Raptopoulou Catherine, Terzis Aris, Stassinopoulou Chariklia I, Chiotellis Efstratios, Pelecanou Maria, Papadopoulos Minas
Institute of Radioisotopes-Radiodiagnostic Products, National Centre for Scientific Research Demokritos, 15310 Athens, Greece.
Inorg Chem. 2003 Sep 8;42(18):5778-84. doi: 10.1021/ic034368j.
The synthesis and characterization of oxotechnetium and oxorhenium mixed-ligand complexes of the general formula MO[NN]S (M = (99)Tc and Re), where NN represents the bidentate ligand 2,2'-bipyridine and S represents a monodentate thiophenol, is reported. The complexes were prepared by ligand exchange reactions using (99)Tc-gluconate and ReOCl(3)(PPh(3))(2) as precursors for the oxotechnetium and oxorhenium complexes, respectively. Compound 1 (M = (99)Tc, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.12(1) A, b = 14.349(6) A, c = 8.801(4) A, beta = 94.81(2) degrees, V = 2918(2) A(3), Z = 4. Compound 3 (M = Re, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.018(9) A, b = 14.421(5) A, c = 8.775(3) A, beta = 94.78(1) degrees, V = 2903(2) A(3), Z = 4. Compound 4 (M = Re, S = 4-methoxythiophenol) crystallizes in the orthorhombic space group Pbca, a = 16.32(1) A, b = 24.55(2) A, c = 16.94(1) A, V = 6788(9) A(3), Z = 8. In all cases, the coordination geometry around the metal is distorted octahedral with the equatorial plane being defined by the three sulfur atoms of the thiophenols and one nitrogen atom of 2,2'-bipyridine, while the apical positions are occupied by the second nitrogen atom of 2,2'-bipyridine and the oxygen of the M=O core. The complexes are stable, neutral, and lipophilic. Complete (1)H and (13)C NMR assignments are reported for all complexes. The analogous oxotechnetium complexes have been also synthesized at tracer level ((99m)Tc) by mixing the 2,2'-bipyridine and the corresponding thiol with Na(99m)TcO(4) generator eluate using NaBH(4) as reducing agent. Their structure was established by chromatographic comparison with authentic oxotechnetium and oxorhenium complexes using high performance liquid chromatography techniques.
报道了通式为MO[NN][S]₃（M = ⁹⁹Tc和Re）的锝氧和铼氧混合配体配合物的合成与表征，其中NN代表双齿配体2,2'-联吡啶，S代表单齿硫酚。这些配合物分别通过配体交换反应制备，使用⁹⁹Tc-葡萄糖酸盐和ReOCl₃(PPh₃)₂作为锝氧和铼氧配合物的前体。化合物1（M = ⁹⁹Tc，S = 4-甲基硫酚）以单斜空间群P2(1)/a结晶，a = 23.12(1) Å，b = 14.349(6) Å，c = 8.801(4) Å，β = 94.81(2)°，V = 2918(2) ų，Z = 4。化合物3（M = Re，S = 4-甲基硫酚）以单斜空间群P2(1)/a结晶，a = 23.018(9) Å，b = 14.421(5) Å，c = 8.775(3) Å，β = 94.78(1)°，V = 2903(2) ų，Z = 4。化合物4（M = Re，S = 4-甲氧基硫酚）以正交空间群Pbca结晶，a = 16.32(1) Å，b = 24.55(2) Å，c = 16.94(1) Å，V = 6788(9) ų，Z = 8。在所有情况下，金属周围的配位几何形状为扭曲八面体，赤道平面由硫酚的三个硫原子和2,2'-联吡啶的一个氮原子定义，而顶端位置由2,2'-联吡啶的第二个氮原子和M=O核心的氧原子占据。这些配合物稳定、中性且具有亲脂性。报道了所有配合物完整的¹H和¹³C NMR归属。类似的锝氧配合物也已在示踪剂水平（⁹⁹mTc）合成，通过将2,2'-联吡啶和相应的硫醇与Na⁹⁹mTcO₄发生器洗脱液混合，使用NaBH₄作为还原剂。通过使用高效液相色谱技术与真实的锝氧和铼氧配合物进行色谱比较，确定了它们的结构。
