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Probing Ionic Association on Metal Oxide Clusters by Pulsed Field Gradient NMR Spectroscopy: The Example of Sn 12 –Oxo Clusters
Author(s) -
Ribot François,
Escax Virginie,
Martins José C.,
Biesemans Monique,
Ghys Laurent,
Verbruggen Ingrid,
Willem Rudolph
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305604
Subject(s) - chemistry , pulsed field gradient , cationic polymerization , diffusion , nuclear magnetic resonance spectroscopy , ionic bonding , ion , spectroscopy , solvent , metal , cluster (spacecraft) , ion exchange , stoichiometry , inorganic chemistry , analytical chemistry (journal) , stereochemistry , molecule , organic chemistry , quantum mechanics , computer science , thermodynamics , programming language , physics
Abstract Pulsed field gradient 1 H NMR spectroscopy has been applied to investigate the association behavior of the Sn 12 –oxo cluster macrocation [(BuSn) 12 O 14 (OH) 6 ] 2+ with two different and smaller anions, p ‐toluenesulfonate (PTS − ) and diphenylphosphinate (Ph 2 PO 2 − ). By monitoring the translational diffusion coefficients of the various species involved, it is shown that the association depends on the anion involved and on the solvent used. Moreover, the possibility to individually monitor the diffusion characteristics of multiple anionic and cationic species in mixtures, by virtue of resolved 1 H resonances available from each species, allows us to evidence the occurrence of ion exchange in such systems. Thus when [(BuSn) 12 O 14 (OH) 6 ](PTS) 2 is mixed with two equivalents of Ph 2 PO 2 NMe 4 , PTS − is displaced by Ph 2 PO 2 − , highlighting the greater affinity of the organotin macrocation for the diphenylphosphinate. This example clearly illustrates the potential of pulsed field gradient 1 H NMR spectroscopy in inorganic/organometallic chemistry, to follow preferential ion pairing in multi‐ion systems at the level of each individually charged species.