Abstract
AbstractThe 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.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.