ISSN:
0009-2940
Keywords:
2,4,6-Trialkylphenol deprotonation
;
Sodium/benzo-15-crown-5 solvation
;
Crystal structure
;
Density functional calculation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The structure of crystals, isolated in low yield, from the attempted metallation of diphenylmethane in tetrahydrofuran solution containing benzo-15-crown-5 at a sodium metal mirror is determined, surprisingly, to be the sodium (benzo-15-crown) salt of 2,6-di(tert-butyl)-4-methylphenol, an antioxidative stabilizer to prevent ether peroxide formation. The structure of the solvent-shared contact ion pair (monoclinic P21/n, Z = 4, R1 = 0.06) proves a strong Na+…O- interaction at the extremely short distance of only 216 pm, a sixfold O-coordination of the Na+ cation in a pentagonal pyramid, and a hemispherical distortion of the crown ether. Density functional calculations at the B3LYP/6-31G* level, based on the structural data, reproduce, within a one-dimensional hypersurface approach, the rather short Na+…O- distance, and predict Mulliken charges of +0.32 for Na′ and -0.71 for 0-, as well as a considerable polarization of the trialkyl phenolate anion.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971301029
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