Sodium cis-tetratolylcyclotetrasiloxanolate and cis-tritolylcyclotrisiloxanolate: Synthesis, structure and their mutual transformations

• Published in: Journal of organometallic chemistry Vol. 823; pp. 103 - 111
• Main Authors: Anisimov, A.A., Zhemchugov, P.V., Milenin, S.A., Goloveshkin, A.S., Tsareva, U.S., Bushmarinov, I.S., Korlyukov, A.A., Takazova, R.U., Molodtsova, Yu.A., Muzafarov, A.M., Shchegolikhina, O.I.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 15.11.2016; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Mutual transformations; Organosiloxanolates; Physical Sciences; Science & Technology; Stereoregular organocyclosiloxanes; Mutual transformations; Stereoregular organocyclosiloxanes; Organosiloxanolates; MESOPHASE STRUCTURE; CRYSTAL-STRUCTURE; RINGS; DECOMPOSITION; POLYMERIZATION; SILANOLATE; THERMAL-BEHAVIOR; SILSESQUIOXANES; LITHIUM COMPOUNDS; SILOXANES
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2016.09.023

Crystalline sodium tolylsiloxanolate anions, based on cis-tritolylcyclotrisiloxanolate, cis-[PhSi(O)O−]3 (1) or cis-tetratolylcyclotetrasiloxanolate, cis-[TolSi(O)O−]4 (2), assembled into a chain or double layer supramolecular structure through coordination with sodium cations and hydrogen bonding contacts have been obtained for the first time. Molecular and crystal structures of {(Na+)3[TolSi(O)O−]3}·7H2O (1a) and {(Na+)4[TolSi(O)O−]4}·7.5n-BuOH (2a), {(Na+)4[TolSi(O)O−]4}·8n-BuOH (2b) have been determined by single-crystal X-ray analysis. The molecular and crystal structures of [(Na+)3[TolSi(O)O−}3]·2H2O (1b) have been determined by X-ray powder diffraction. The mutual transformation of the compounds into each other has been demonstrated. Reaction of the sodium salts with chlorotrimethylsilane resulted in the formation of the corresponding cis-tri[(tolyl)(trimethylsiloxy)]cyclotrisiloxane, cis-[TolSi(O)(OSiMe3)]3 (3), and cis-tetra[(tolyl)(trimethylsiloxy)]cyclotetrasiloxane, cis-[TolSi(O)(OSiMe3)]4 (4), in high yield. Their molecular and crystalline structures have been confirmed by single crystal X-ray analysis, NMR spectroscopy, and mass spectrometry. Crystalline sodium tolylsiloxanolates and their TMS- derivatives were synthesized. Molecular and crystal structures were determined by single-crystal X-ray analysis and X-ray powder diffraction. The mutual transformation of the compounds into each other has been demonstrated. [Display omitted]