Sensing the chirality of Dawson lanthanide polyoxometalates [α1-LnP2W17O61]7- by multinuclear NMR spectroscopy

被引：54

作者：

Boglio, Cecile ^{[1
,2
]}

Hasenknopf, Bernold ^{[2
]}

Lenoble, Geraldine ^{[2
]}

Remy, Pauline ^{[1
,2
]}

Gouzerh, Pierre ^{[2
]}

Thorimbert, Serge ^{[1
]}

Lacote, Emmanuel ^{[1
]}

Malacria, Max ^{[1
]}

Thouvenot, Rene ^{[2
]}

机构：

[1] Univ Paris 06, Inst Chim Mol FR 2769, Lab Chim Organ,CNRS, UMR 7611, F-75252 Paris 05, France

[2] Univ Paris 06, Inst Chim Mol FR 2769, Lab Chim Inorgan & Mat Mol,CNRS, UMR 7071, F-75252 Paris 05, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 05期

关键词：

chirality; lanthanides; NMR spectroscopy; polyoxometalates; tungsten;

D O I：

10.1002/chem.200701429

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Lanthanide complexes of the chiral Dawson phosphotungstate [alpha(1)-P2W17O61](10-) were used to study the formation of diastereomers with optically pure organic ligands. The present work started with the full assignment of the W-183 NMR spectra of [alpha(1)-Yb-W17O61](7-) at different temperatures and concentrations, which allowed the structure of the dimerized form in aqueous solution to be established. Different enantiopure amino acids and phosphonic acids were screened as ligands. Both types allowed chiral differentiation by multinuclear NMR spectroscopy under fast-exchange conditions. Functional groups with a good affinity for the oxo framework of the polyoxometalate were identified, and maps of the interactions between L-serine and N-phosphono-methyl-L-proline with [alpha(1)-Yb-(H2O)(4)P2W17O61](7-) were established. This demonstrates the power of W-183 NMR spectroscopy to elucidate the molecular recognition of inorganic molecules by organic compounds. N-Phosphonomethyl-L-proline appears to be a convenient ligand to promote separation of the diastereomers and ultimately resolution of the enantiomers of [alpha(1)-Yb(H2O)(4)P2W17O61](7-).

引用

页码：1532 / 1540

页数：9

共 63 条

[1] SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE DETERMINATION OF A NOVEL CHIRAL HETEROPOLYANION - THE 3-1 OCTADECATUNGSTOHEXAPHOSPHATE [J].