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Polydentate amine and ether solvates of lithium hexamethyldisilazide (LiHMDS): Relationship of ligand structure, relative solvation energy, and aggregation state
6Li, 15N, and 13C NMR spectroscopic investigations of [6Li, 15N]lithium hexamethyldisilazide ([6Li, 15N]-LiHMDS) coordinated by 29 polyamines, polyethers, and aminoethers reveal a range of structural types including eta1-coordinated mono- and disolvated dimers, eta2-coordinated (3-coordinate) monomers, eta1,eta2-coordinated (4-coordinate) monomers, eta2,eta2-coordinated (5-coordinate) monomers, polymers (linked dimers), triple ions, and solvent-separated ion pairs. Ligand binding constants on the LiHMDS monomers shed light on chelate ring size and steric effects, aza- and oxaphilicity, mechanisms and rates of ligand substitution, and the ‘macrocyclic effect’.
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Chiral Catalysts,
Chiral catalysts – SlideShare