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  

Biomemic Synthesis, Crystal Structure of Molybdenum and Tungsten Chiral Octahedral Complex(NH_3CH_2CH_2CH_2NH_2)_2[Mo_(0.4)W_(0.6)O_2(C_6H_4O_2)_2] and Its Interaction with ATP by ~1H, ^(13)C,^(31)P and ^(15)N NMR

作　　者：鲁晓明[1] 邓元[1] 李丽[1] 姜凌[2] 毛希安[2] 叶朝辉[2] 

机构地区：[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

出　　处：《高等学校化学学报》2005年第4期611-616,共6页Chemical Journal of Chinese Universities

基　　金：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.

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.A chiral octahedral molybdenum complex(NH_3CH_2CH_2CH_2NH_2)_2[Mo_~0.4 W_~0.6 O_2(C_6H_4O_2)_2] was obtained by the reaction of tetra-butyl ammonium β-octamolybdate with catechole and 1,3-diaminopropane in the mixed solvent of CH_3OH and CH_3CN, 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 D_2O but were oxidized to M(Ⅵ) and almost part of catecholato ligands dissociated with the central metals while it is mixed with ATP in D_2O. 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.

关 键 词：钼钨手性八面体配合物 晶体结构 ATP NMR 

分 类 号：O614[理学—无机化学]