RHENIUM(VI) OXO COMPLEXES RELEVANT TO TECHNETIUM RENAL IMAGING AGENTS DERIVED FROM MERCAPTOACETYLGLYCYLGLYCYLAMINOBENZOIC ACID ISOMERS - STRUCTURAL AND MOLECULAR MECHANICS STUDIES
RHENIUM(VI) OXO COMPLEXES RELEVANT TO TECHNETIUM RENAL IMAGING AGENTS DERIVED FROM MERCAPTOACETYLGLYCYLGLYCYLAMINOBENZOIC ACID ISOMERS - STRUCTURAL AND MOLECULAR MECHANICS STUDIES
复制标题
DOI：
10.1021/ic00039a026
复制
发表时间：
1992-06-24
影响因子：
4.6
通讯作者：
MARZILLI, LG
中科院分区：
文献类型：
--
作者：
HANSEN, L;CINI, R;MARZILLI, LG
报道了三种由巯基乙酰基甘氨酰氨基苯甲酸(MAG2-ABAH5)异构体衍生的Re(V)氧配合物的合成和表征。由邻氨基苯甲酸、间氨基苯甲酸和对氨基苯甲酸合成了不同的异构体，但末端羧基的位置不同。8-10的阴离子[REO(MAG2-*ABAH)]-(*=Para(8)，Meta(9)，Oro(10))含有羧基质子化的四阴离子形式的配体。通过ReOCl3(Me2SO)(Ph3P)在温和条件下的交换反应合成了8、9和10，分别分离为[Ph4P]+、[Bu4N]+和[Ph4P]+盐。用X-射线衍射法测定了8和10的结构，除了羧基的位置外，其余结构都很相似。配位构型为假正方锥体，氮和硫施主原子形成一个正方形的碱基，氧配体在顶端。10中羧基的取向与Re=O基团相反。化学式C37H33N3O7PReS，a=10.985(5)埃，b=12.320(5)埃，c=14.417(8)埃，α=93.67(4)度，β=104.78(4)度，伽马=104.78(3)度，V=1787.9(14)埃，三斜晶系，空间群P1bar，Z=2。10的晶体数据：化学式C37H31N3O6PRes，a=11.066(4)埃，b=19.436(7)埃，c=16.495(6)埃，β=107.73(3)度，V=3379.4(11)埃m~3，单斜晶系，空间群P2(1)/c，Z=4。由于8和10中的羧基被质子化，以及这类放射性药物的其他相关结构，包括[Ph4As][TCO(MAG3H)](MAG3H=四阴离子的硫代乙酰甘氨酸)，我们开发了分子力学参数，使我们能够计算8，10和[TCO(MAG3H)]-的结构。然后，我们将计算扩展到所有三个去质子化的异构体配合物和[TCO(MAG3)]2-，以近似它们的溶液相结构。我们得出结论，[TCO(MAG3)]2-物种在构象上是灵活的，我们已经对结构与肾脏清除率进行了初步评估。
The synthesis and characterization of three rhenium(V) oxo complexes derived from isomers of mercaptoacetylglycylglycylaminobenzoic aminobenzoic acid (MAG2-ABAH5) are reported. The isomers were synthesized from o-, m- and p-aminobenzoic acid and differed in the position of the terminal carboxyl group. The anions of 8-10, [ReO(MAG2-*ABAH)]- (* = para (8), meta (9), ortho (10)), contained the tetraanionic form of the ligands with the carboxyl group protonated. 8, 9, and 10 were synthesized by exchange reactions of ReOCl3(Me2SO)(Ph3P) under moderate conditions and were isolated as [Ph4P]+, [Bu4N]+, and [Ph4P]+ salts, respectively. The structures of 8 and 10 were determined by X-ray diffraction methods; except for the location of the carboxyl group, the structures are similar. The coordination geometry is pseudo square pyramidal, with nitrogen and sulfur donor atoms forming a square base and the oxo ligand at the apex. The orientation of the carboxyl group in 10 is anti to the Re=O group. Crystal data for 8: chemical formula C37H33N3O7PReS, a = 10.985 (5) angstrom, b = 12.320 (5) angstrom, c = 14.417 (8) angstrom, alpha = 93.67 (4)-degrees, beta = 106.63 (4)-degrees, gamma = 104.78 (3)-degrees, V = 1787.9 (14) angstrom3, triclinic, space group P1BAR, Z = 2. Crystal data for 10: chemical formula C37H31N3O6PReS, a = 11.066 (4) angstrom, b = 19.436 (7) angstrom, c = 16.495 (6) angstrom, beta = 107.73 (3)degrees, V = 3379.4 (11) angstrom3, monoclinic, space group P2(1)/c, Z = 4. Since the carboxyl groups are protonated in 8 and 10 and in other relevant structures from this class of radiopharmaceuticals including [Ph4As][TcO(MAG3H)] (MAG3H = tetraanionic form of mercaptoacetyltriglycine), we developed molecular mechanics parameters that allowed us to calculate the structures of 8, 10, and [TcO(MAG3H)]-. We then extended the calculations to all three isomeric complexes in their deprotonated forms and to [TcO(MAG3)]2- in order to approximate their solution phase structures. We conclude that the [TcO(MAG3)]2- species is conformationally flexible, and we have made an initial assessment of structures vs renal clearance.