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change of procedure, namely to use toluene/Et N and THF/NaH, as ence and Technology (DST), New Delhi (grant number CS-099/
3
described below, led to crystals of 3 obtained from a mixture of
products. As elemental analyses would not be useful, the NMR spec-
tra of the crude and isolated crystals have been provided in the
Supporting Information (see Figures S5–S8).
2
012) for providing financial support.
Keywords: Mannich bases · Tin · Silicon · Cage
compounds · X-ray diffraction
In a second attempt, a two-necked flask containing toluene (30 mL)
was charged with H L (1.00 g, 3.00 mmol) and triethylamine
3
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(1.28 mL, 9.1 mmol) along with a magnetic bar and the mixture
was stirred for 1 h. Phenyltrichlorostannane (0.918 g, 3.00 mmol) in
dry toluene was added dropwise into the flask and stirring was
continued for 5 h at room temperature. The white precipitate of
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[
[
[
[
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Et N·HCl formed during the reaction was filtered and the filtrate
3
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evaporated under vacuum to obtain a white solid. The crude prod-
uct was recrystallized from acetonitrile.
In a third attempt, compound 3 was prepared from the reaction of
H3L with NaH. In this procedure, excess NaH (0.27 g, 11.2 mmol)
was washed (with hexane to remove oil) and added to a two-
necked flask along with THF (30 mL) and then a solution of H3L
[
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(
0.50 g, 1.5 mmol) in THF (20 mL) was added slowly. This solution
was stirred for 2 h and then phenyltrichlorostannane (0.45 g,
.5 mmol) dissolved in dry THF was added dropwise to the flask
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1
and further stirred for 5 h. Subsequently, the NaCl formed and ex-
cess NaH were removed by filtration and the filtrate was evaporated
under vacuum to afford 3 as a white solid. The product was crystal-
lized from acetonitrile.
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[
[
[
[
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Data for the crude product obtained in the third attempt; yield
2010, 48, 1122–1132.
0
.98 g, m.p. 250–260 °C (decomp.). IR: ν˜ = 1610 (C–C), 1474 (C=C),
–1
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Commun. 2008, 94–96.
1
259 (C–O), 1161 (C–N), 542 (Sn–O), 500 (Sn–C), 452 (Sn←N) cm .
119
Sn NMR (149 MHz, CDCl ): δ = –97, –275, –282, –503, –533, –538,
3
[
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–558, –582 ppm.
1
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Wiegand, Y. Wang, V. Jouikov, K. Jurkschat, Inorg. Chem. 2012, 51, 1041–
1056.
Data for isolated crystals: H NMR (400 MHz, CDCl ): δ = 2.12 (s,12
3
3
a,b
3
1
1
2 1
H, Ar-CH3 ), 2.85 [t, J( H- H) = 6.12 Hz, 2 H, NCH C], 3.14 [d, J( H-
2
[
1
3
1
1
H) = 12.8 Hz, 2 H, NCH Ar], 3.20 [t, J( H- H) = 6.12 Hz, 2 H, OCH C],
2
2
1
2
1
1
4
1
1
4
.30 [d, J( H- H) = 12.8 Hz, 2 H, NCH Ar], 6.46 [s, J( H- H) = 4.0 Hz,
2
4
1
1
3 1
2
H, 2,8-H], 6.75 [s, J( H- H) = 4.0 Hz, 2 H, 6,12-H], 6.97 [t, J( H-
1
3 1
H) = 8.0 Hz, 2 H, 22,28-H], 7.01–7.03 (m, 1 H, 16-H), 7.08 [t, J( H-
H) = 8.0 Hz, 4 H, 21,23,27,29-H], 7.22–7.24 (m, 2 H, 15,17-H), 7.47
dd, J( H- Sn) = 73.9, J( H- Sn) = 89.3, J( H- H) = 8.0, J( H- H) =
1
1
117
1
119
3
1
1
4
1
1
[
1
1
1
117
1
119
.4 Hz, 2 H, 20,24,26,30-H], 7.75 [dd, J( H- Sn) = 91.8, J( H- Sn) =
07.8, 3J( H- H) = 8.0, J( H- H) = 1.4 Hz, 2 H, 14,18-H] ppm.
1
1
4
1
1
13
[22] N. Srivastav, R. Singh, V. Kaur, RSC Adv. 2015, 5, 62202–62213.
C
[
[
23] O. Wichmann, H. Sopo, E. Colacio, A. J. Mota, R. Sillanpää, Eur. J. Inorg.
Chem. 2009, 4877–4886.
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NMR (100 MHz, CDCl ): δ = 16.6 (Ar-CH ), 20.1 (Ar-CH b), 31.0
a
3
3
3
(
NCH C), 58.4 (NCH Ph), 61.4 (NCH Ph), 67.0 (OCH C), 121.3 (C-3,9),
2 2 2 2
1
1
2
4
(
[
23.7 (C-5,11), 125.2 (C-22,28), 126.2 (C-16), 126.7 (C-21,23,27,29),
27.4 (C-15,17), 127.9 (C-2,8), 128.2 (C-1,7), 128.4 (C-6,12), 129.0 (C-
0,24,26,30), 129.5 (C-14,18), 130.5 (C-25), 135.8 (C-13), 158.4 (C-
6
4, 2606–2617.
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2547–2557.
,10) ppm. 1 Sn (149 MHz, CDCl ): δ = –282, –538 ppm. MS: m/z
19
[26] E. Safaei, H. Sheykhi, T. Weyhermüller, E. Bill, Inorg. Chim. Acta 2012, 384,
3
+
+
69–75.
%) = 74 (8.65) [Ph] , 135 (4.69) [CH (Me C H )OH] , 196 (9.21)
2 2 6 2
+
[27] E. Lauren, H. Kivela, M. Hanninen, A. Lehtonen, Polyhedron 2009, 28,
NH(CH CH OH)CH (Me C H )OH + H] , 524 (23.13) [M/2 – Ph SnO
2 2 2 2 6 2 2
+
+
+
4051–4055.
+
1
H] , 546 (100) [M/2 – Ph SnO + Na] , 1425 (0.73) [M – 2Ph] ,
2 2
[
28] J. Hakala, R. Sillanpaa, A. Lehtonen, Inorg. Chem. Commun. 2012, 21, 21–
3.
+
472 (0.40) [M – 2Ph] .
2
[
[
29] Y. Kim, J. G. Verkade, Organometallics 2002, 21, 2395–2399.
30] S. Padmanabhan, S. Katao, K. Nomura, Organometallics 2007, 26, 1616–
Supporting Information (see footnote on the first page of this
article): 1D chain structure of compound 3, proposed mechanism
for the formation of 3, X-ray crystallographic data for 1–3, coordina-
tion environment around Si and Sn, planar view of Sn4O4 in 3,
1
626.
[
31] J. Lee, Y. Hong, J. H. Kim, S. H. Kim, Y. Do, Y. K. Shin, Y. Kim, J. Organomet.
Chem. 2008, 693, 3715–3721.
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33] H. Sopo, J. Sviili, A. Valkonen, R. Sillanpää, Polyhedron 2006, 25, 1223–
119
1
Sn and H NMR spectra for 3.
[
[
1
232.
[34] O. Wichmann, H. Sopo, A. Lehtonen, R. Sillanpää, Eur. J. Inorg. Chem.
011, 1283–1291.
Acknowledgments
2
The authors are thankful to the University Grants Commission
[
35] A. L. Johnson, M. G. Davidson, Y. Perez, M. D. Jones, N. Merle, P. R. Raithby,
(
UGC), New Delhi [17-06/2012 (i) EU-V] and Department of Sci-
S. P. Richards, Dalton Trans. 2009, 5551–5558.
Eur. J. Inorg. Chem. 2016, 1730–1737
www.eurjic.org
1736
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