期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 82, 期 12, 页码 6223-6231出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.7b00800
关键词
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资金
- NSF [1464538]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1464538] Funding Source: National Science Foundation
We report the direct measurement of ligand-binding constants of organolithium complexes using a H-1 NMR/diffusion-ordered NMR spectroscopy (DOSY) titration technique. Lithium hexamethyldisilazide complexes with ethereal and ester donor ligands (THF, diethyl ether, MTBE, THP, tent-butyl acetate) are characterized using H-1 NMR and X-ray crystallography. Their aggregation and solvation states are confirmed, using diffusion coefficient-formula weight correlation analysis, and the H-1 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.
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