Synthesis and f-element ligation properties of NCMPO-decorated pyridine N-oxide platforms.
Synthesis and f-element ligation properties of NCMPO-decorated pyridine N-oxide platforms.
复制标题
NCMPO 修饰的吡啶 N-氧化物平台的合成和 f 元件连接特性。
DOI：
10.1039/c3dt53611d
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发表时间：
2014
影响因子：
4
通讯作者：
L. Delmau
中科院分区：
文献类型：
--
作者：
Sabrina Ouizem;Daniel Rosario;D. Dickie;R. Paine;A. Bettencourt;B. Hay;Julien Podair;L. Delmau
2-{[2-（2-甲氧基苯基）氨基]-乙基}-1-甲基-N，N，N-二甲基甲酰胺的分步合成（二苯基磷酰基）乙酰氨基]甲基}吡啶1-氧化物，2-[Ph 2 P（O）CH 2C（O）N（H）CH 2] C5 H4 NO（6），2-{[2-（二苯基磷酰基）乙酰氨基]甲基}-6-[（二苯基磷酰基）甲基]吡啶1-氧化物，2-[Ph 2 P（O）CH 2C（O）N（H）CH 2]-6-[Ph 2 P（O）CH 2] C5 H3 NO（7）和2，6-二{[2-报道了一种新的吡啶氧化物2，6-[Ph_2P（O）CH_2C（O）N（H）CH_2]_2C_5H_3NO（8），并对6·2H_2O、7和2进行了沿着光谱表征和单晶X-射线衍射结构测定。6-[Ph 2 P（O）CH 2C（O）N（H）CH 2] 2C 5 H3 N·MeOH 18·MeOH，8的吡啶前体。分子力学计算表明，6，7和8应该经历最小的空间位阻给体基团重组，这将允许三齿，四齿和五齿对接结构的镧系元素阳离子上的相应配体。然而，对镧系配合物{[Yb（6）（NO3）3]·（MeOH）}n，{[Lu（6）（NO3）3]·（MeOH）} n，[Er（6）2（H2O）2]（NO3）3·（H2O）4}n，{[La（13）（NO3）3（MeOH）]·（MeOH）}n，{[Eu（7）（NO3）2（EtOAc）0.5（H2O）0.5]（NO3）}2·MeOH和[Dy 3（7）4（NO3）4（H2O）2]（NO3）5·（MeOH）5·（H2O）2显示了混合的螯合/桥联配体：Ln（III）相互作用的固态结构，其使用低于最大密度的配体。6和7与Eu（III）在固态和在MeOH溶液中的结合也通过发射光谱来获得。本文研究了硝酸介质中Eu（Ⅲ）和Am（Ⅲ）在1，2-二氯乙烷中的萃取行为，并与正辛基（苯基）-N，N-二异丁基氨甲酰基甲基氧化膦（OPhDiBCMPO，1b）和2-[（二苯基）膦酰基甲基]吡啶N-氧化物（DPhNOPO，4a）的萃取行为进行了比较。
Stepwise syntheses of 2-{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]C5H4NO (6), 2-{[2-(diphenylphosphoryl)acetamido]methyl}-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide, 2-[Ph2P(O)CH2C(O)N(H)CH2]-6-[Ph2P(O)CH2]C5H3NO (7) and 2,6-bis{[2-(diphenylphosphoryl)acetamido]methyl}pyridine 1-oxide, 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3NO (8), are reported along with spectroscopic characterization data and single crystal X-ray diffraction structure determination for 6·2H2O, 7 and 2,6-[Ph2P(O)CH2C(O)N(H)CH2]2C5H3N·MeOH 18·MeOH, the pyridine precursor of 8. Molecular mechanics computations indicate that 6, 7 and 8 should experience minimal steric hindrance to donor group reorganization that would permit tridentate, tetradentate and pentadentate docking structures for the respective ligands on lanthanide cations. However, crystal structure determination for the lanthanide complexes, {[Yb(6)(NO3)3]·(MeOH)}n, {[Lu(6)(NO3)3]·(MeOH)}n, [Er(6)2(H2O)2](NO3)3·(H2O)4}n, {[La(13)(NO3)3(MeOH)]·(MeOH)}n, {[Eu(7)(NO3)2(EtOAc)0.5(H2O)0.5](NO3)}2·MeOH and [Dy3(7)4(NO3)4(H2O)2](NO3)5·(MeOH)5·(H2O)2 reveal solid-state structures with mixed chelating/bridging ligand : Ln(III) interactions that employ lower than the maximal denticity. The binding of 6 and 7 with Eu(III) in the solid state and in MeOH solutions is also accessed by emission spectroscopy. The acid dependence for solvent extractions with 6 and 7 in 1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solutions is described and compared with the behavior of n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OPhDiBCMPO, 1b) and 2-[(diphenyl)phosphinoylmethyl]pyridine N-oxide (DPhNOPO, 4a).