Eu(Ⅲ)与Hbbimp的配合物的合成、表征及与活化磷酸二酯键模型物BDNPP的水解动力学研究Synthesis and Characterization of Bieuropium Complex Coordinating Hbbimp, and Its Hydrolytic Kinetic Research for Cleaving an Activated Phosphate Diester BDNPP
周春琼,高飞,李树娥,杨频
摘要(Abstract)：
合成了Eu(Ⅲ)配合物[Eu2(bbimp)(CH3COO)(CH3CH2O)2(CH3CH2OH)](ClO4)2(A),产物经IR谱、UV谱、1HNMR谱、摩尔电导、元素分析对其结构进行了基本鉴定。用紫外光谱法研究了磷酸二酯键模型物双 (2,4 二硝基苯基)磷酸盐BDNPP与配合物A在pH7.26,25和37℃时,[BDNPP]=[A]=2.5×10-5mol·L-1时的动力学性质,得到BDNPP的二级水解速率常数为k25℃=3.027×103(mol·L-1)-1·min-1,k37℃=6.060×103(mol·L-1)-1·min-1,半衰期t1 2分别为12.9和6.6min,使BDNPP的水解速率大大提高。
关键词(KeyWords)： 无机化学;Hbbimp;Eu(Ⅲ)配合物;BDNPP;紫外光谱;水解;稀土
基金项目(Foundation): 国家自然科学基金(20171031)资助项目;; 山西省自然科学基金资助项目
作者(Author): 周春琼,高飞,李树娥,杨频
参考文献(References)：
- [1] StraterN,LipsombWN,KlablunderT,etal. Two metalioncatalysisinenzymaticacyl andphosphoryl transferreactions[J].Angew.Chem.Int.Ed.Engl.,1995,35:2024.
- [2] WilcoxD. BinuclearMetallohydrolases[J].Chem.Rev.,1996,96:2435.
- [3] WillianH,ChaomaJR,BreslowR. Selectivehydrolysisofphosphateesters,nitrophenylphosohatesandUPU,bydimericzinccomplexesdependsonthespacerlength[J].J.Am.Chem.Soc.,1995,117:562.
- [4] WallM,RosemaryCH,ChinJ. Doublelewisacidactivationinphosphatediestercleavage[J].Angew.Chem.Int.Ed.Engl.,1993,32(11):1633.
- [5] SchnaithlMT,HansongS,LawrenceQJr. Double strandedcleavageofPBR322byadiioncomplexviaa"hydrolytic"mechanism[J].Proc.Natl.Acad.Sci.USA.,1994,91:569.
- [6] RagunathanKG,SchneiderHJ. Binuclearlanthanidecomplexesascatalystsforthehydrolysisofbis(P nitrophenyl) phosphateanddouble strandedDNA[J].Angew.Chem.Int.Ed.Engl.,1996,35:1219.
- [7] 朱 兵,赵大庆,倪嘉缵. 稀土及其配合物对核酸的断裂作用[J].化学进展,1998,10:395.
- [8] MarkEB,AdrianneKT,LawrenceQJR,etal. Doublestrandhydrolysisofplasmidbydiceriumcomplexesat37℃[J].J.Am.Chem.Soc.,2001,123:1898.
- [9] HildePB,DouglaswS. Towardscopper(Ⅱ)hemocyaninmodels:thesynthesisandmolecularstructureofabinuclearCopper(Ⅱ)complexofaheptadentateligand[J].Inorg.Chemi.Acta,1985,99:L53.
- [10] HildePB,DouglaswS. TowardsCopper(Ⅱ)hemocyaninmodels:synthesisandcharacterizationofabinuclearcopper(Ⅱ)complexofaheptadentateligand[J].Inorg.Chem.,1987,26:749.
- [11] SuzukiM,KanatomiH,MuraseI. DinuclearCobalt(Ⅱ)complexeswithvariousligandsandtheirdioxgencomplexes[J].Bull.Chem.Soc.Jpn.,1984,57:36.
- [12] GearyWJ. TheUseofconductivitymeasurementsinorganicsolventsforthecharacterisationofcoordinationcompounds[J].Coor.Chem.Rev.,1971,7:81.
- [13] DeaconGB,PhillipsRJ. Relationshipsbetweenthecarbonoxygenstretchingfrequenciesofcarboxylatocomplexesandthetypeofcarboxylatecoordination[J].Coor.Chem.Rev.,1980,33:227.
- [14] RaptaM,KamarasP,BrewerGA,etal. Coordinationmodesofwater derivedbridgingligandsindiiron(Ⅲ)complexes:stablizationofanoxo hydroxobridgebyhydrogenbonding[J].J.Am.Chem.Soc.,1995,117:12865.
- [15] YoungMJ,WahnonD,ChinJ,etal. ReactivityofCopper(Ⅱ)hydroxidesandCopper(II)alkoxidesforcleavinganactivatedphosphatediester[J].J.Am.Chem.Soc.,1995,117:9441.
- [16] BrowneKA,BruiceTC. Chemistryofphosphodiesters,DNAandmodels.2.Thehydrolysisofbis(8 hydroxyquinoLine)phosphateintheabsenceandpresenceofmetalions[J].J.Am.Chem.Soc.,1992,114:4951.
- [17] BelleC,Gautier LuneauI,PierreJ,etal. Aphenoxo briggeddiferriccomplexwithtwodifferentcoordinationnumbersintwodistinctcoordinationsites[J].Inorg.Chem.,1996,35:3706.