Premium
Dynamic Phenomena in Self‐Complementary {2}‐Metallocryptates Probed by Solution 133 Cs‐NMR. New Insights into Ion Pairing Processes: X‐Ray Structure and Solid‐State NMR Spectra of a Meandering Species
Author(s) -
Maid Harald,
Heinemann Frank W.,
Scheurer Andreas,
Mooren Nicolai,
Saalfrank Rolf W.,
Bauer Walter
Publication year - 2012
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201200494
Subject(s) - chemistry , nmr spectra database , solid state nuclear magnetic resonance , monomer , nuclear magnetic resonance spectroscopy , metal , yield (engineering) , two dimensional nuclear magnetic resonance spectroscopy , proton nmr , spectral line , crystallography , solvent , ion , analytical chemistry (journal) , carbon 13 nmr , polymer , stereochemistry , nuclear magnetic resonance , organic chemistry , physics , materials science , astronomy , metallurgy
Two self‐complementary {2}‐metallocryptates, differing in methyl and phenyl substituents, respectively, have been studied by X‐ray analysis, and solid‐state and solution NMR. Mixed Mg/Cs metal methyl complex 2 is a linear polymer in the solid state. The two different Cs sites are confirmed by 133 Cs‐solid‐state NMR. By contrast, the analog mixed Mg/Cs metal phenyl complex 4 is a meandering polymer as shown by an actual X‐ray analysis. The four non‐equivalent Cs‐sites in 4 are reflected in the solid‐state NMR spectra. Solution 133 Cs‐NMR spectra of 4 reveal two independent dynamic processes: a fast exchange of Cs within contact ion‐pairs and solvent‐separated ion‐pairs (CIP, SSIP), and a slower exchange of ‘inside’ endo Cs, surrounded by three ligands, and ‘outside’ exo Cs involved in the CIP/SSIP equilibrium. Complete line‐shape analysis of variable‐temperature 133 Cs‐NMR spectra of 4 yield kinetic parameters of=10.8 kcal/mol for the fast SSIP‐CIP exchange and =13.2 kcal/mol for the slower endo / exo exchange of Cs. DOSY‐NMR Measurements confirm the monomeric nature of 4 in solution.