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Russian Chemical Bulletin

, Volume 68, Issue 2, pp 380–388 | Cite as

Sterically hindered tetrylenes based on new 1,10-phenanthroline-containing diols: initiators for ε-caprolactone polymerization

  • B. N. Mankaev
  • K. V. Zaitsev
  • G. S. Zaitseva
  • A. V. Churakov
  • M. P. Egorov
  • S. S. KarlovEmail author
Full Articles

Abstract

Previously unknown tetradentate ONNO-type ligands 15 (4,7-di(4-R´-phenoxy)-2,9- di(HOCR2CH)-1,10-phenanthrolines (R´ = Me, R–R = –(CH2)5– (1), R = Me (2), R–R = 2,2-adamantylene (3); R´ = But, R–R = –(CH2)5– (4), R = Me (5)) were synthesized by sequential treatment of 2,9-dimethyl-4,7-di(4-R´-phenoxy)-1,10-phenanthrolines 6 (R´ = Me) and 7 (R´ = But) with excess LDA and appropriate dialkyl ketone. The structure of compound 4 was determined by single-crystal X-ray diffraction. Previously uncharacterized phenanthroline 6 was synthesized by the treatment of 4,7-dichloro-2,9-dimethyl-1,10-phenanthroline with excess p-cresol in the presence of KOH. The reaction of compounds 15 with one equivalent of Lappert´s germylene or stannylene, M[N(SiMe3)2]2 (M = Ge, Sn), gave the corresponding germylenes 812 (M = Ge, R´ = Me, R–R = –(CH2)5– (8), R = Me (9), R–R = 2,2-adamantylene (10), R´ = But, R2 = –(CH2)5– (11), R = Me (12)) and stannylenes 1317 (M = Sn, R´ = Me, R–R = –(CH2)5– (13), R = Me (14), R–R = 2,2-adamantylene (15), R´ = But, R–R = –(CH2)5– (16), R2 = Me (17)) in satisfactory yields. According to 1H, 13C, and 119Sn NMR data, the synthesized stannylenes are monomeric in solution, and the tin atom has a coordination number of 4. In the series of the compounds under consideration, stannylene 16 proved to be the most active initiator for e-caprolactone polymerization, whereas the germylenes were shown to be inactive in this process.

Key words

germanium tin germylenes stannylenes tetrylenes ring-opening polymerization poly-ε-caprolactone 

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Copyright information

© Springer Science+Business Media, Inc. 2019

Authors and Affiliations

  • B. N. Mankaev
    • 1
    • 2
  • K. V. Zaitsev
    • 1
    • 2
  • G. S. Zaitseva
    • 1
    • 2
  • A. V. Churakov
    • 1
    • 3
  • M. P. Egorov
    • 1
  • S. S. Karlov
    • 1
    • 2
    Email author
  1. 1.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.Department of ChemistryM. V. Lomonosov Moscow State UniversityMoscowRussian Federation
  3. 3.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation

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