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SiMe3), –12 to –20 (2 × SiMe3) (1), –20.7 (Si(SiMe3)2cyclic),
–33.3 (Si(SiMe3)2linear); 17b: H NMR (C6D6) δ: 7.37 (br s),
4.09, 3.96, 3.45, 3.32, 3.13, 2.62, 2.59, 2.48, 2.35, 2.29,
2.16, 1.36 (all SiMe3 and OSiMe3, 17c–17f); 29Si NMR
1
7.07–7.28 (br m) (all PhH), 6.71 (s, 1H, SiC(H) = CSi), 5.50
(br s, 1H, C=CH2), 5.00 (br s, 1H, C=CH2), 4.53 (br s, 1H,
MeOCH), 4.28 (br s, 1H, Me3SiOCH), 3.85 (d, 1H, PhCH,
J = 1.8 Hz), 3.16 (s, 3H, MeO), 1.65–2.40 (br m, all Ad-
CH), 0.60 (s, 9H, SiMe3), 0.50 (s, 9H, SiMe3), 0.49 (s, 9H,
SiMe3), 0.38 (s, 9H, SiMe3), 0.28 (s, 9H, OSiMe3linear), 0.03
(s, 9H, OSiMe3cyclic); 13C NMR (C6D6) δ: 159.46 (SiC(H) =
CSi), 150.47 (C=CH2), 143.24 (SiC(H) = CSi), 137.11 (br s,
i,o-PhC), 127.50, 127.43, 126.48 (all PhC), 115.07 (C=CH2),
103.8 (Me3SiOCcyclic) (11), 82.48 (Me3SiOCH), 81.22
(MeOCH), 65.83 (PhCH), 56.26 (MeO), 42.19 (4° Ad-
Ccyclic), 41.17, 40.93, 40.15, 37.30, 37.18, 29.22 (all Ad-C)
(12), 5.53 (OSiMe3cyclic), 4.21 (SiMe3), 3.56 (SiMe3), 3.02
(SiMe3), 2.62 (OSiMe3linear), 2.26 (SiMe3) (13); 29Si NMR
(C6D6) δ 13.5 (OSiMe3linear), 5.8 (OSiMe3cyclic), –15.3, –16.8
(2 × SiMe3), –12 to –20 (2 × SiMe3) (14), –21.1
(Si(SiMe3)2cyclic), –33.3 (Si(SiMe3)2) (14). 17a and 17b: HR
EI-MS for C53H98O3Si8 (M+) (m/z): calcd. 1006.5670, found
1006.5639. 17c–17f (colourless crystals): IR (cm–1) 2905
(s), 2852 (m), 1452 (m), 1248 (s), 1102 (m), 1039 (s), 1000
(C6D6) δ: 13.6 (OSiMe3linear, 17c), 13.5–13.7 (OSiMe3linear
,
,
17d–17f) (14), 6.0 (OSiMe3cyclic, 17e), 2.1–2.3 (OSiMe3cyclic
17d, 17f) (14), 2.2 (OSiMe3cyclic, 17c), –11.0, –13.4 (2 ×
SiMe3cyclic, 17c), –16.0, –17.0 (2 × SiMe3, 17c), –13 to –18
(SiMe3, 17d–17f) (14), –29.1 (Si(SiMe3)2, 17e), –31.5, –31.9
(2 × Si(SiMe3)2, 17c), –33.9 (Si(SiMe3)2, 17d) (16). 17c–
17f: HR EI-MS for C53H98O3Si8 (M+) (m/z): calcd.
1006.5670, found 1006.5631. 18a and 18b (white solid): IR
(cm–1) 2906 (m), 2851 (w), 1650 (m), 1499 (w), 1451 (w),
1250 (m), 1093 (m), 1035 (m), 836 (s), 752 (w), 698 (w);
1
18a: H NMR (C6D6) δ: 7.59–7.61 (m, 2H, o-PhH), 7.21–
7.26 (m, 2H, m-PhH), 7.06–7.11 (m, 1H, p-PhH), 6.04 (s,
2
1H, SiC(H) = C, JH-Si = 8.8 Hz), 3.35 (d, 1H, MeOCH, J =
7.2 Hz), 3.29 (s, 3H, MeO), 2.68 (d, 1H, PhCH, J = 7.2 Hz),
1.97–2.10, 1.79–1.85, 1.67–1.74 (m, Ad-CH), 1.47 (s, 3H,
Me), 0.37 (s, 9H, SiMe3), 0.33 (s, 9H, SiMe3) (17), 0.297 (s,
9H, OSiMe3); 13C NMR (C6D6) δ: 167.81 (SiC(H) = C),
137.25 (i-PhC), 131.06 (o-PhC), 128.2 (m-PhC) (11), 126.78
(SiC(H) = C), 126.09 (p-PhC), 97.64 (Me3SiOC), 70.88
(MeOCH), 58.76 (MeO), 42.9 (4° Ad-C) (11), 40.30 (Ad-C),
37.21 (Ad-C), 31.65 (CMe), 31.53 (PhCH), 29.55 (Ad-C),
13.01 (Me), 3.51 (OSiMe3), 1.93 (SiMe3), 1.53 (SiMe3); 29Si
NMR (C6D6) δ: 6.5 (OSiMe3), –12 to –13 (2 × SiMe3) (14),
1
(w), 837 (s), 746 (w), 683 (w); H NMR (C6D6) δ: 7.92–
7.96, 7.06–7.33 (br m, all PhH, 17c–17f), 6.72 (s, 1H,
SiC(H) = CSi, 17c), 6.58 (s, 1H, SiC(H) = CSi, 17d), 6.53
(s, 1H, SiC(H) = CSi, 17e), 6.42 (s, 1H, SiC(H) = CSi, 17f),
5.66 (s, 1H, C=CH2, 17d), 5.60 (s, 1H, C=CH2, 17d), 5.50
(s, 1H, C=CH2, 17c), 5.43 (s, 1H, C=CH2, 17c), 5.40 (s, 1H,
C=CH2, 17f), 5.30 (s, 1H, C=CH2, 17e), 4.87 (d, 1H,
MeOCH, J = 6.0 Hz, 17c), 4.81 (s, 1H, C=CH2, 17f) (15),
4.78 (d, 1H, MeOCH, J = 7.2 Hz, 17d), 4.75 (br s, 1H,
MeOCH, 17e), 4.72 (br s, 1H, C=CH2, 17e), 4.68 (s, 1H,
MeOCH, 17f) (15), 4.38 (s, 1H, Me3SiOCH, 17f), 4.35 (s,
1H, Me3SiOCH, 17e), 4.34 (s, 1H, Me3SiOCH, 17d), 4.33
(s, 1H, Me3SiOCH, 17c), 4.11 (s, 1H, PhCH, 17e), 4.10 (s,
1H, PhCH, 17f), 3.75 (d, 1H, PhCH, J = 6.6 Hz, 17d), 3.65
(d, 1H, PhCH, J = 6.0 Hz, 17c), 3.36 (s, 3H, MeO, 17f),
3.30 (s, 3H, MeO, 17e), 3.14 (s, 3H, MeO, 17c), 3.11 (s, 3H,
MeO, 17d), 1.46–2.13 (br m, all Ad-CH, 17c–17f), 0.63,
0.59, 0.58, 0.564, 0.56, 0.55, 0.543, 0.535, 0.52, 0.42, 0.38,
0.33, 0.28, 0.27, 0.268, 0.266, 0.26 (s, all SiMe3 and
OSiMe3, 17c–17f); 13C NMR (C6D6) δ: 162.0 (SiC(H) =
CSi, 17e) (11), 161.57 (SiC(H) = CSi, 17c and 17d), 155.9
(C=CH2, 17d) (11), 155.09 (C=CH2, 17c), 150.6 (C=CH2,
17e) (11), 144.80 (SiC(H) = CSi, 17c), 143.23 (SiC(H) =
CSi, 17d), 142.75 (SiC(H) = CSi, 17e), 141.23 (i-PhC, 17d),
141.02 (i-PhC, 17c), 139.41 (i-PhC, 17e), 134.46, 134.32
(17c), 134.07 (17d), 133.32 (17c), 133.02, 132.81 (17e),
127.23, 127.17 (17c), 126.96, 126.73, 126.56, 126.47,
126.24 (17c), 126.06 (all PhC, 17c–17f), 120.33 (C=CH2,
17e), 116.91 (C=CH2, 17d), 116.30 (C=CH2, 17c), 99.81
(Me3SiOCcyclic, 17c), 97.93 (Me3SiOCcyclic, 17d), 94.72
(Me3SiOCcyclic, 17e), 84.03 (MeOCH, 17e), 83.07 (MeOCH,
17d), 82.76 (Me3SiOCH, 17e), 82.67 (MeOCH, 17c), 82.37
(Me3SiOCH, 17c), 80.17 (Me3SiOCH, 17d), 64.53 (PhCH,
17e), 62.55 (PhCH, 17d), 61.05 (PhCH, 17c), 57.12 (MeO,
17d), 56.66 (MeO, 17c), 56.20 (MeO, 17e), 43.9 (4° Ad-C,
17d) (11), 43.64 (4° Ad-C, 17e), 43.48 (4° Ad-C, 17c),
41.11, 40.97, 40.75, 40.23, 39.89, 37.18, 37.10, 37.04,
36.90, 32.30, 30.16, 30.10, 29.79, 29.37, 29.29, 29.05 (all
Ad-C, 17c–17f), 6.27, 6.19, 5.90, 5.08, 4.61, 4.20, 4.16,
1
–27.0 (Si(SiMe3)2); 18b: H NMR (C6D6) δ: 7.65–7.66 (m,
2H, o-PhH), 7.21–7.26 (m, 2H, m-PhH), 7.06–7.11 (m, 1H,
2
p-PhH), 5.96 (s, 1H, SiC(H) = C, JH-Si = 9.2 Hz), 3.93 (d,
1H, MeOCH, J = 7.2 Hz), 3.25 (s, 3H, MeO), 2.20 (d, 1H,
PhCH, J = 7.2 Hz), 1.97–2.10, 1.79–1.85, 1.67–1.74 (m, Ad-
CH), 1.51 (s, 3H, Me), 0.36 (s, 9H, SiMe3), 0.32 (s, 9H,
SiMe3) (17), 0.303 (s, 9H, OSiMe3); 13C NMR (C6D6) δ:
168.73 (SiC(H) = C), 137.25 (i-PhC), 130.72 (o-PhC), 128.2
(m-PhC) (11), 126.09 (p-PhC), 125.35 (SiC(H) = C), 98.06
(Me3SiOC), 68.39 (MeOCH), 58.47 (MeO), 42.0 (4° Ad-C)
(11), 40.30 (Ad-C), 38.17 (PhCH), 37.21 (Ad-C), 30.83
(CMe), 29.55 (Ad-C), 11.27 (Me), 3.51 (OSiMe3), 1.93
(SiMe3), 1.53 (SiMe3); 29Si NMR (C6D6) δ: 6.5 (OSiMe3),
–12 to –13 (2 × SiMe3), –25.8 (Si(SiMe3)2); 18a, 18b: HR
EI-MS for C33H56O2Si4 (M+) (m/z): calcd. 596.3357, found
596.3370.
General procedure for the addition of alkynes to silene
14
Excess alkyne 1a or 1c (1.5–4 equiv.) dissolved in hex-
anes or ether was added to silene 14 dissolved in the same
solvent (8). The reaction mixture was left to stir overnight.
The solvent was removed and the residue was placed under
high vacuum to remove the excess alkyne. The residue was
1
analyzed by H NMR spectroscopy.
Acknowledgements
We thank the Natural Sciences and Engineering Research
Council of Canada (NSERC), the University of Western On-
tario, and the Ontario Photonics Consortium for financial
support.
References
1. H. Ottosson and P.G. Steel. Chem. Eur. J. 12, 1576 (2006).
© 2008 NRC Canada