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

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Abstract

Previously unknown tetradentate ONNO-type ligands 1–5 (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 1–5 with one equivalent of Lappert´s germylene or stannylene, M[N(SiMe3)2]2 (M = Ge, Sn), gave the corresponding germylenes 8–12 (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 13–17 (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.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    B. N. Mankaev, K. V. Zaitsev, G. S. Zaitseva, A. V. Churakov, M. P. Egorov & S. S. Karlov

  2. Department of Chemistry, M. V. Lomonosov Moscow State University, 1, Build. 3, Leninskie Gory, 119991, Moscow, Russian Federation

    B. N. Mankaev, K. V. Zaitsev, G. S. Zaitseva & S. S. Karlov

  3. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    A. V. Churakov

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  1. B. N. Mankaev
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  2. K. V. Zaitsev
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  3. G. S. Zaitseva
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  4. A. V. Churakov
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  5. M. P. Egorov
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  6. S. S. Karlov
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Correspondence to S. S. Karlov.

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Dedicated to Corresponding Member of the Russian Academy of Sciences G. I. Nikishin on the occasion of his 90th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0380–0388, February, 2019.

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Mankaev, B.N., Zaitsev, K.V., Zaitseva, G.S. et al. Sterically hindered tetrylenes based on new 1,10-phenanthroline-containing diols: initiators for ε-caprolactone polymerization. Russ Chem Bull 68, 380–388 (2019). https://doi.org/10.1007/s11172-019-2396-4

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  • DOI: https://doi.org/10.1007/s11172-019-2396-4

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