The [Cu(tmen)(OH)(OH2)](+) promoted hydrolysis of 2,4-dinitrophenyl diethyl phosphate and O-isopropyl methylphosphonofluoridate (sarin) (tmen = N,N,N ' N '-tetramethyl-1,2-diaminoethane)

Hay RW.; Govan N.

首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >The [Cu(tmen)(OH)(OH2)](+) promoted hydrolysis of 2,4-dinitrophenyl diethyl phosphate and O-isopropyl methylphosphonofluoridate (sarin) (tmen = N,N,N ' N '-tetramethyl-1,2-diaminoethane)

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The [Cu(tmen)(OH)(OH2)](+) promoted hydrolysis of 2,4-dinitrophenyl diethyl phosphate and O-isopropyl methylphosphonofluoridate (sarin) (tmen = N,N,N ' N '-tetramethyl-1,2-diaminoethane)

机译：[Cu（tmen）（OH）（OH2）]（+）促进了2,4-二硝基苯基二乙基磷酸酯和O-异丙基甲基氟膦酸酯（sarin）的水解（tmen = N，N，N'N'-N'-tetramethyl-1， 2-二氨基乙烷）

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The hydrolysis of the phosphate triester 2,4-dinitrophenyl diethyl phosphate to diethyl phosphate is catalysed by [Cu(tmen)(OH)(OH2)](+) in the pH range 6.5 to 8.0. At pH 7 with a catalyst concentration of 2.5 x 10(-3) mol dm(-3) the rate enhancement is ca 10(4) fold. The pH dependence of the catalysis is consistent with the hydroxoaqua complex being the active species in the hydrolysis. The greater kinetic effectiveness of this weak base, compared with hydroxide ion on a molar basis, indicates a bifunctional mechanism in which bound hydroxide acts as a nucleophile in conjunction with electrophilic catalysis by copper at the phosphoryl oxygen. The copper complex is an excellent catalyst for the hydrolysis of O-isopropyl methylphosphonofluoridate (Sarin). At pH 7 and 25 degrees C using a Sarin concentration of 4.5 x 10(-2) mol dm(-3) and a [Cu(tmen)(OH2)(2)](2+) concentration of 5 x 10(-3) mol dm(-3), complete hydrolysis (9 turnovers) occurs in 13 min. (C) 1998 Elsevier Science Ltd. All rights reserved. [References: 18]

机译：通过[Cu（tmen）（OH）（OH2）]（+）在pH 6.5至8.0范围内将磷酸三酯2,4-二硝基苯基二乙基磷酸水解为磷酸二乙基酯。在pH为7且催化剂浓度为2.5 x 10（-3）mol dm（-3）的情况下，速率提高约10（4）倍。催化的pH依赖性与羟肟酸络合物是水解中的活性物质相一致。与基于摩尔的氢氧根离子相比，该弱碱的更大的动力学有效性表明了一种双功能机理，其中结合的氢氧根与亲铜在磷酰氧处的亲电催化作用一起充当亲核试剂。铜络合物是水解O-异丙基甲基膦酰氟（Sarin）的极佳催化剂。在pH 7和25摄氏度下，使用Sarin浓度为4.5 x 10（-2）mol dm（-3）和[Cu（tmen）（OH2）（2）]（2+）浓度为5 x 10（- 3）mol dm（-3），在13分钟内发生完全水解（9次）。（C）1998 Elsevier ScienceLtd。保留所有权利。 [参考：18]

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |1998年第12期|共7页
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Hay RW.; Govan N.;
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1. The [Cu(tmen)(OH)(OH2)](+) promoted hydrolysis of 2,4-dinitrophenyl diethyl phosphate and O-isopropyl methylphosphonofluoridate (sarin) (tmen = N,N,N ' N '-tetramethyl-1,2-diaminoethane) [J] . Hay RW., Govan N. Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1998,第11a12期

机译：[Cu（tmen）（OH）（OH2）]（+）促进了2,4-二硝基苯基二乙基磷酸酯和O-异丙基甲基氟膦酸酯（sarin）的水解（tmen = N，N，N'N'-N'-tetramethyl-1， 2-二氨基乙烷）
2. A LANTHANUM MACROCYCLE CATALYSED HYDROLYSIS OF 2,4-DINITROPHENYL DIETHYL PHOSPHATE AND O-ISOPROPYL METHYLFLUOROPHOSPHONATE (SARIN) [J] . Hay RW., Govan N. Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1997,第24期

机译：镧大分子催化的2,4-二苯二甲酸二乙酯磷酸酯和邻-异丙基甲基氟膦酸酯（SARIN）的水解
3. The [Cu([9]aneN(3))(OH)(OH2)](+) catalysed hydrolysis of the phosphotriester 2,4-dinitrophenyl diethyl phosphate ([9]aneN(3)=1,4,7-triazacyclononane) [J] . Hay RW., Govan N. Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1998,第4期

机译：[Cu（[9] aneN（3））（OH）（OH2）]（+）催化磷酸三酯2,4-二硝基苯基二乙基磷酸酯（[9] aneN（3）= 1,4,7-三氮杂环壬烷的水解）
4. Kinetics and Mechanism of Hydrolysis of a Model Phosphate Diester by Cu(Me3tacn)(OH2)22+ (Me3tacn = 1, 4, 7-Trimethyl-1, 4, 7-triazacyclononane) [O] . -1

机译：Cu（ME3TACN）（OH2）2 2+（ME3TACN = 1,4,7-三甲基-1,4,7-三氮杂环烷的水模型磷酸二酯水解的动力学和机理
5. Hydrolysis of 2,4-Dinitrophenyl Phosphate in Normal and Reverse Micelles [R] . DelRosso, F., Bartoletti, A., DiProfio, P., 1995

机译：正磷酸酯和反胶束中2,4-二硝基苯基磷酸酯的水解

The [Cu(tmen)(OH)(OH2)](+) promoted hydrolysis of 2,4-dinitrophenyl diethyl phosphate and O-isopropyl methylphosphonofluoridate (sarin) (tmen = N,N,N ' N '-tetramethyl-1,2-diaminoethane)

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