FERRIC ION SEQUESTERING AGENTS .23. SYNTHESIS OF TRIS(HYDROXYPYRIDINETHIONE) LIGANDS AND THEIR FERRIC COMPLEXES - X-RAY STRUCTURE-ANALYSIS OF N,N',N''-TRIS((1,2-DIDEHYDRO-1-HYDROXY-2-THIOXOPYRID-6-YL)CARBONYL)-2,2',2''-TRIAMINO-TRIETHYLAMINATO)IRON(III)
FERRIC ION SEQUESTERING AGENTS .23. SYNTHESIS OF TRIS(HYDROXYPYRIDINETHIONE) LIGANDS AND THEIR FERRIC COMPLEXES - X-RAY STRUCTURE-ANALYSIS OF N,N',N''-TRIS((1,2-DIDEHYDRO-1-HYDROXY-2-THIOXOPYRID-6-YL)CARBONYL)-2,2',2''-TRIAMINO-TRIETHYLAMINATO)IRON(III)
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DOI：
10.1021/ic00003a033
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发表时间：
1991-02-06
影响因子：
4.6
通讯作者：
RAYMOND, KN
中科院分区：
文献类型：
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作者：
ABUDARI, K;RAYMOND, KN
以2-巯基吡啶-6-羧酸、1-氧化物和三胺为原料，在DMF中与羧酸和1，1‘-甲酰基二咪唑生成的活性酰胺反应，合成了六齿硫代羟氨酸酯配体。分离得到的三胺类化合物为N，N‘，N’‘-tris((1，2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-2，2’，2‘’-triaminotriethylamine，N，-N‘，N’‘-tris((1，2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-1，-5，10-三氮杂环烷和1，3，5-tris((N-methyl-N-((1，2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)amino)methyl)benzene.通过元素分析、红外光谱和核磁共振光谱对这些配体进行了表征，并合成了铁络合物。用单晶自动计数器X射线衍射法测定了N，N‘，N’‘-tris((1，2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-2，2’，2‘’-triaminotriethylaminato)iron(III).0.5CHCl3的结构。该化合物属三斜空间群Plbar，晶胞参数为：z=4，a=11.073(1)埃，b=13.858(1)埃，c=22.401(2)埃，α=70.216(8)度，β=71.847(8)度，伽马=68.104(8)度。两个结晶学上独立的铁络合物分子和一个无序的氯仿分子在不对称单元中。用F(O)2和Gt；3-sigma-(F(O))2进行6,000次反射的全矩阵最小二乘精化，所有非氢原子都给定各向异性温度因子，收敛到R=0.040和R(W)=0.058。铁离子周围的配位多面体介于八面体和三棱柱几何构型之间，类似于1-羟基-2(1H)-吡啶酮的铁络合物。
Hexadentate thiohydroxamate ligands derived from 2-mercaptopyridine-6-carboxylic acid 1-oxide and triamines have been prepared by reaction of the amines with the active amide produced from the carboxylic acid and 1,1'-carbonyldiimidazole in DMF. The triamides isolated are N,N',N''-tris((1,2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-2,2',2''-triaminotriethylamine, N,-N',N''-tris((1,2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-1,-5,10-triazadecane, and 1,3,5-tris((N-methyl-N-((1,2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)amino)methyl)benzene. These ligands have been characterized by their elemental analyses and IR and NMR spectra, and the ferric complexes have also been prepared and characterized. The structure of the complex N,N',N''-tris((1,2-didehydro-1-hydroxy-2-thioxopyrid-6-yl)carbonyl)-2,2',2''-triaminotriethylaminato)iron(III).0.5CHCl3 has been determined by single-crystal automated-counter X-ray diffraction. The complex crystallizes in the triclinic space group PlBAR with z = 4, a = 11.073 (1) angstrom, b = 13.858 (1) angstrom, c = 22.401 (2) angstrom, alpha = 70.216 (8)-degrees, beta = 71.847 (8)-degrees, gamma = 68.104 (8)-degrees. Two crystallographically independent molecules of the ferric complex and one disordered chloroform molecule are in the asymmetric unit. Full-matrix least-squares refinement using 6000 reflections with F(o)2 > 3-sigma-(F(o))2, with all non-hydrogen atoms given anisotropic temperature factors, converged to R = 0.040 and R(W) = 0.058. The coordination polyhedron around the ferric ion is intermediate between octahedral and trigonal-prismatic geometries and is similar to that of the ferric complex of 1-hydroxy-2(1H)-pyridinone.