Al, Ti complexes in ringꢀopening polymerization
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 7, July, 2016
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34.81 (C(8)CMe3, C(4)CMe3); 43.79 (br, C(15)H2); 55.52 (br,
NC(12)H2, NC(14)H2), 81.69, 82.14 (TiOCMe3), 124.45, 126.69,
127.07, 127.96, 135.90, 159.28 (carbon atoms of the aromatic
rings). Found (%): C, 69.21; H, 9.28; N, 2.58. C34H55TiNO4.
Calculated (%): C, 69.25; H, 9.40; N, 2.38.
2. J. Wu, T.ꢀL. Yu, C.ꢀT. Chen, C.ꢀC. Lin, Coord. Chem. Rev.,
2006, 250, 602.
3. K. V. Zaitsev, S. S. Karlov, A. A. Selina, Yu. F. Oprunenko,
A. V. Churakov, B. Neumüller, J. A. K. Howard, G. S. Zaitꢀ
seva, Eur. J. Inorg. Chem., 2006, 1987.
6,6ꢀDi(tertꢀbutoxy)ꢀ2,4,8,10ꢀtetra(tertꢀbutyl)ꢀ13ꢀethylꢀ13,14ꢀ
dihydroꢀ12Hꢀ5,7ꢀdioxaꢀ13ꢀazaꢀ6ꢀtitanadibenzo[a,f]cyclodecaꢀ
diene (6) was obtained similarly to complex 5 starting from ligand
2 (0.23 g, 0.48 mmol) and Ti(OBut)4 (0.16 g, 0.48 mmol). Comꢀ
plex 6 (0.30 g, 96%) was obtained as a yellow powder. 1H NMR
(CDCl3), δ: 0.80—0.90 (m, 3 H, MeC(15)H2); 1.28 (s, 18 H,
C(2)But, C(10)But); 1.39 (s, 9 H, TiOBut); 1.47 (s, 27 H, TiOBut
and C(4)But, C(8)But, overlap of two signals); 2.71—2.85 (m, 2 H,
C(15)H3); 3.63 (br.s, 2 H, NC(12/14)H2); 3.93 (d, 2 H,
NC(14/12)H2, J = 11.7 Hz); 6.91 (s, 2 H, C(1)H, C(11)H);
7.20 (s, 2 H, C(3)H, C(9)H). 13C NMR (CDCl3), δ: 5.80
(MeC(15)H2); 29.82 (C(2)CMe3, C(10)CMe3); 31.71 (TiOCMe3,
C(4)CMe3, C(8)CMe3, overlap of two signals); 32.18 (TiOCMe3);
34.19, 35.10 (C(4)CMe3 C(8)CMe3); 45.29 (br, C(15)H2); 54.96
(br, NC(12)H2, NC(14)H2); 82.98, 84.10 (OCMe3); 122.88,
123.93, 124.32, 135.03, 140.43, 159.21 (carbon atoms of the aroꢀ
matic rings). Found (%): C, 71.72; H, 9.96; N, 2.04. C40H67TiNO4.
Calculated (%):C, 71.30; H, 10.02; N, 2.08.
4. K. V. Zaitsev, M. V. Bermeshev, A. A. Samsonov, Yu. F.
Oprunenko, A. V. Churakov, J. A. K. Howard, S. S. Karlov,
G. S. Zaitseva, New J. Chem., 2008, 32, 1415.
5. M. Huang, E. Kh. Lermontova, K. V. Zaitsev, A. V. Churakꢀ
ov, Yu. F. Oprunenko, J. A. K. Howard, S. S. Karlov, G. S.
Zaitseva, J. Organomet. Chem., 2009, 694, 3828.
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G. S. Zaitseva, S. S. Karlov, J. Polym. Sci., Part A: Polym.
Chem., 2010, 48, 1230.
7. M. Huang, M. M. Kireenko, K. V. Zaitsev, Yu. F. Oprunenꢀ
ko, A. V. Churakov, J. A. K. Howard, M. V. Zabalov, E. Kh.
Lermontova, J. Sundermeyer, T. Linder, S. S. Karlov, G. S.
Zaitseva, J. Organomet. Chem., 2012, 706—707, 66.
8. M. M. Kireenko, E. A. Kuchuk, K. V. Zaitsev, V. A. Tafeenꢀ
ko, Y. F. Oprunenko, A. V. Churakov, E. Kh. Lermontova,
G. S. Zaitseva, S. S. Karlov, Dalton Trans., 2015, 44, 11963.
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2004, 37, 7968.
Xꢀray diffraction study of compounds 3 and 6 was performed
on a Bruker SMART APEX II automated diffractometer (MoKα
radiation, λ = 0.71073 Å, graphite monochromator, ωꢀscan techꢀ
nique). Correction for adsorption was introduced based on the
measurements of intensities of equivalent reflections.26 The
structures were solved by direct method; all the nonhydrogen
atoms (except of disordered But groups in 6) were refined by the
fullꢀmatrix anisotropic least squares method on F2 (SHELXTL27).
In compound 6, the tertꢀbutyl groups containing the atoms C(3)
and C(7) are rotationally disordered over two positions with the
occupancy ratios of 0.66/0.34 and 0.54/0.46, while the group,
containing the atom C(41) is disordered similarly, but over three
positions (0.46/0.32/0.22). All three groups were refined with
10. A. J. Chmura, M. G. Davidson, M. D. Jones, M. D. Lunn,
M. F. Mahon, Dalton Trans., 2006, 887.
11. A. J. Chmura, M. G. Davidson, M. D. Jones, M. D. Lunn,
M. F. Mahon, A. F. Johnson, P. Khunkamchoo, S. L. Robꢀ
erts, S. S. F. Wong, Macromolecules, 2006, 39, 7250.
12. C.ꢀT. Chen, C.ꢀA. Huang, B.ꢀH. Huang, Dalton Trans.,
2003, 3799.
13. O. Wichmann, R. Sillanpää, A. Lehtonen, Coord. Chem. Rev.,
2012, 256, 371.
14. L. M. AlcazarꢀRoman, B. J. O´Keefe, M. A. Hillmyer, W.B.
Tolman, Dalton Trans., 2003, 3082.
15. L.ꢀC. Liang, S.ꢀT. Lin, C.ꢀC. Chien, J. Chin. Chem. Soc.,
2013, 60, 710.
16. E.Y. Tshuva, I. Goldberg, M. Kol, Z. Goldschmidt, Inorg.
Chem., 2001, 40, 4263.
17. L.ꢀC. Liang, S.ꢀT. Lin, C.ꢀC. Chien, Inorg. Chem., 2013, 52, 1780.
18. K. Phomphrai, P. Chumsaeng, P. Sangtrirutnugul, P. Kongꢀ
saeree, M. Pohmakotr, Dalton Trans., 2010, 39, 1865.
19. Z. Tang, V. C. Gibson, Eur. Polym. J., 2007, 43, 150.
20. Y. Sarazin, R. H. Howard, D. L. Hughes, S. M. Humphrey,
M. Bochmann, Dalton Trans., 2006, 340.
21. D. Peri, C. M. Manna, M. Shavit, E. Y. Tshuva, Eur. J.
Inorg. Chem., 2011, 2011, 4896.
22. S. Barroso, P. Adгo, M. T. Duarte, A. Meetsma, J. C. Pesꢀ
soa, M. W. Bouwkamp, A. M. Martins, Eur. J. Inorg. Chem.,
2011, 4277.
23. E. Safaei, M. Rasouli, T.Weyhermüller, E. Bill, Inorg. Chim.
Acta, 2011, 375, 158.
24. A. R. Hutchison, A. Mitra, D. A. Atwood, Main Group Chem.,
2005, 4, 187.
25. J. S. Klitzke, T. Roisnel, E. Kirillov, O. L. Casagrande, J.ꢀF.
Carpentier, Organometallics, 2014, 33, 5693.
26. G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
27. G. M. Sheldrick, SADABS, Program for scaling and correction of
area detector data, University of Göttingen, Germany, 1997.
...
the imposition of restrictions on the C—Me and Me Me disꢀ
tances (SADI). In the structure 3, all the hydrogen atoms were
found from the difference Fourier synthesis and refined isotropiꢀ
cally, whereas in the structure 6 all the hydrogen atoms were
placed in the calculated position and refined using a riding
scheme. The experimental details are given in Table 4.
Xꢀray diffraction studies were performed in the Multiꢀ
access Center of the N. S. Kurnakov Institute of General
and Inorganic Chemistry of the Russian Academy of Sciꢀ
ences. The structure 3 and 6 were deposited with the Camꢀ
bridge Crystallographic Data Center (CCDC 1439269 and
1439270, respectively).
Organoaluminum compounds were synthesized and
studied with the financial support of the Russian Science
Foundation (Project No. 14ꢀ33ꢀ00017). The synthesis and
studies of organotitanium compounds were financially
supported by the Russian Foundation for Basic Research
(Project ofiꢀm 13ꢀ03ꢀ12054). The studies were carried out
using equipment purchased at the expense of the Development
Program of the M. V. Lomonosov Moscow State University.
References
1. O. DechyꢀCabaret, B. MartinꢀVaca, D. Bourissou, Chem.
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Received February 4, 2016;
in revised form May 18, 2016