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Ligand Binding Constants to Lithium Hexamethyldisilazide Determined by Diffusion-Ordered NMR Spectroscopy.
- Source :
-
Journal of Organic Chemistry . 6/16/2017, Vol. 82 Issue 12, p6223-6231. 9p. - Publication Year :
- 2017
-
Abstract
- We report the direct measurement of ligand-binding constants of organolithium complexes using a ¹H NMR/diffusion-ordered NMR spectroscopy (DOSY) titration technique. Lithium hexamethyldisilazide complexes with ethereal and ester donor ligands (THF, diethyl ether, MTBE, THP, tert-butyl acetate) are characterized using ¹H NMR and X-ray crystallography. Their aggregation and solvation states are confirmed using diffusion coefficient-formula weight correlation analysis, and the ¹H NMR/DOSY titration technique is applied to obtain their binding constants. Our work suggests that steric hindrance of ethereal ligands plays an important role in the aggregation, solvation, and reactivity of these complexes. It is noteworthy that diffusion methodology is utilized to obtain binding constants. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00223263
- Volume :
- 82
- Issue :
- 12
- Database :
- Academic Search Index
- Journal :
- Journal of Organic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 124292429
- Full Text :
- https://doi.org/10.1021/acs.joc.7b00800