高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (4): 611.

• 研究论文 • 上一篇    下一篇

1,3-丙二胺邻苯二酚钼钨手性八面体配合物的仿生合成、晶体结构以及与ATP作用的液相NMR研究

鲁晓明1, 邓元1, 李丽1, 姜凌2, 毛希安2, 叶朝辉2   

  1. 1. 首都师范大学化学系, 北京 100037;
    2. 中国科学院武汉物理与数学研究所, 武汉 430071
  • 收稿日期:2004-06-21 出版日期:2005-04-10 发布日期:2005-04-10
  • 通讯作者: 鲁晓明(1955年出生),女,教授,主要从事结构化学、配位化学和波谱学研究.E-mail:Lu2xiaoming@126.com E-mail:Lu2xiaoming@126.com
  • 基金资助:

    国家自然科学基金(批准号:20271034);北京市自然科学基金(批准号:2012005)资助.

Biomemic Synthesis, Crystal Structure of Molybdenum and Tungsten Chiral Octahedral Complex(NH3CH2CH2CH2NH2)2[Mo0.4W0.6O2(C6H4O2)2] and Its Interaction with ATP by 1H, 13C,31P and 15N NMR

LU Xiao-Ming1, DENG Yuan1, LI Li1, JIANG Ling2, MAO Xi-An2, YE Chao-Hui2   

  1. 1. Department of Chemistry, Capital Normal University, Beijing 100037, China;
    2. Wuhan Institute of Physics and Mathematics, Chinese Academy of Science, Wuhan 430071, China
  • Received:2004-06-21 Online:2005-04-10 Published:2005-04-10

摘要: 合成了1,3-丙二胺邻苯二酚钼钨手性八面体配合物(NH3CH2CH2CH2NH2)2[Mo0.4W0.6O2(C6H4O2)2],并对其进行了单晶结构解析,研究了其与ATP作用的液相NMR谱.该晶体属正交晶系,空间群为Pcan.晶胞参数a=0.7501(2)nm,b=2.3994(7)nm,c=1.2178(4)nm,Z=4.[Mo0.4W0.6O2(C6H4O2)2]2-的配位几何构型为手性八面体,晶体为外消旋体.配位阴离子中MoW中心金属离子除了与两个端基O配位形成cis-MO键外,同时还分别与两个邻苯二酚配位基团的的氧原子配位,形成4个M—Ob(M=Mo,W)键,构成两个五元环.利用1HNMR,13CNMR,31PNMR以及1H-15NHMBC对标题配合物及其与ATP在D2O溶剂中的作用进行了研究,发现标题配合物的MoW中心金属离子在纯D2O溶剂中被还原成+5价,但与ATP混合后转化为+6价,且与原配位基邻苯二酚发生解离.解离后的[MO2]2+最大可能与腺嘌呤上的氨基N原子配位,而此配位可能是其抗癌抗肿瘤活性的主要作用机理之一.

关键词: 钼钨手性八面体配合物, 晶体结构, ATP, NMR

Abstract: A chiral octahedral molybdenum complex(NH3CH2CH2CH2NH2)2[Mo<sup>0.4 W<sup>0.6 O2(C6H4O2)2] was obtained by the reaction of tetra-butyl ammonium β-octamolybdate with catechole and 1,3-diaminopropane in the mixed solvent of CH3OH and CH3CN, characterized by X-ray diffraction, and its interaction with ATP was studied by 1H, 13 C, 31 P and 15 N NMR. The crystal is orthorhombic with space group Pcan, a=0.750 1(2) nm, b=2.399 4(7) nm, c=1.217 8(4) nm, Z=4. The central metal ion exhibits distorted octahedral coordination with cis dioxo catechole. The 1H and 13 C NMR studies reveal that the central metals were reduced to M(Ⅴ) and a little catecholato ligand was hydrolyzed when the complex is dissolved in D2O but were oxidized to M(Ⅵ) and almost part of catecholato ligands dissociated with the central metals while it is mixed with ATP in D2O. The shift of the 1H, 13 C, 31 P and 15 N chemical shifts in adenine of ATP suggest that there is a coordinated interaction between central metal and the N atoms in adenine, and the coordination might be responsible for the anti-tumor and DNA cleavage activities of the title complex.

Key words: Molybdenum and tungsten chiral oitahedral complex, Crystal structure, NMR, ATP

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