Preparation of [G-2]16-exo-4-[C≡CCH2CH2O]-10-MeBPI (10)
106.8 (C-3), 119.0 (C-5), 121.2 (C-9), 123.6 (C-6), 126.4 (C-11),
130.4 (C-1), 139.9 (C-2), 151.1 (C-10), 151.5 (C-7/C-8), 152.7 (C-
A solution of LDA in thf (2 M) (0.76 ml = 1.52 mmol) was
slowly added to a solution of 4-(3-butynoxy)-10-MeBPI (2a)
(0.30 g = 0.76 mmol) in thf (30 ml), which was cooled to
−80 ◦C. The mixture was warmed to −40 ◦C and then re-cooled
to −80 ◦C. After the addition of [G-2]16-exo-Cl (0.14 g = 43.3
lmol) the reaction mixture was warmed to room temperature
and then stirred for another 24 h. After removal of the volatiles
in vacuo, the residue was washed with 3 × 10 ml of water and
then extracted with n-hexane until the extracts were colourless.
The pure reaction product was obtained as a yellow amorphous
solid.
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12), 153.6 (C-7/C-8), 161.7 (C-4). { H} Si-NMR (79.5 MHz,
CDCl3, 298 K): d = −8.7 (≡C–Si). IR (KBr): m [cm−1] = 2954 (w),
2922 (w), 2857 (w), 2164 (vw), 1582 (s), 1519 (m), 1470 (s), 1405
(vw), 1364 (m), 1329 (vw), 1296 (w), 1232 (w), 1188 (w), 1106
(w), 1088 (vw), 1020 (w), 933 (vw), 885 (vw), 825 (m), 808 (m),
776 (w), 679 (vw). C30H34ClN5OPdSi (650.58 g.mol−1): calcd.: C
55.39, H 5.27, N 10.76; found: C 54.93, H 4.91, N 10.45.
Yield: 0.29 g (32.9 lmol, 76%). Mp: 54 ◦C. 1H-NMR
(300.17 MHz, CDCl3, 298 K): d = −0.05 (s, 12 H, H(m)), −0.04
(s, 24 H, H(i)), 0.15 (s, 96 H, H(e)), 0.68 (m, 112 H, H(f), H(h),
H(j), H(l), H(n), H(p)), 1.42 (m, 56 H, H(g), H(k), H(o)), 2.33
(s, br, 96 H, 10-CH3), 2.74 (m, br, 32 H, H(b)), 4.17 (m, br, 32 H,
H(a)), 6.86 (m, br, 32 H, H(11)), 7.07 (m, br, 16 H, H(5)), 7.20 (s,
br, 32 H, H(9)), 7.44 (s, br, 16 H, H(3)), 7.85 (m, br, 16 H, H(6)),
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13
8.38 (m, br, 32 H, 1H(2)), 13.79 (s, br, 16 H, NH). { H} C-
NMR (75.5 MHz, CDCl3, 298 K): d = −4.9 (C-i, C-m), −1.5
(C-e), 18.3–19.9 (C-f, C-g, C-h, C-j, C-k, C-l, C-n, C-o, C-p),
20.8 (C-b), 20.9 (10-CH3), 66.5 (C-a), 86.1 (C-c), 102.4 (C-d),
106.4 (C-3), 119.4 (C-5), 120.9/121.1 (C-9), 123.4/123.5 (C-11),
123.6 (C-6), 128.4 (C-1), 137.9 (C-2), 147.3 (C-12), 148.9 (C-
10), 153.4 (C-7), 160.3/160.5 (C-8), 161.7 (C-4). { H} Si-NMR
(79.5 MHz, CDCl3, 298 K): d = −17.7 (≡C–Si), 0.8/0.9/1.1
(Si(CH2)4–, Si(CH3)–). IR (KBr): m [cm−1] = 3428 (m, br), 2912
(m), 2875 (w), 2177 (m), 1633 (s), 1590 (s), 1543 (m), 1487 (m),
1465 (m), 1401 (vw), 1358 (w), 1328 (w), 1280 (w), 1242 (m), 1162
(m), 1039 (m), 910 (w), 818 (m), 716 (vw). MS (MALDI-TOF):
m/z = 8963.2 [M]−. C512H620N80O16Si29 (8965.56 g.mol−1): calcd.:
C 68.59, H 6.97, N 12.49; found: C 68.60, H 7.16, N 12.37.
[G-2]1-endo-4-[C≡CCH2CH2O]-10-MeBPIPdCl (12)
Yield: 55.0 mg (30.1 lmol, 56%). 1H-NMR (300.17 MHz,
CD2Cl2, 298 K): d = −0.02 (s, 81 H, H(k)), 0.57 (m, br, 48 H,
H(e), H(g), H(h), H(j)), 1.35 (m, 24 H, H(f), H(i)), 2.42 (s, br,
6 H, 10-CH3), 2.79 (t, 3JHH = 7.3 Hz, 2 H, H(b)), 4.24 (t, 3JHH
=
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7.3 Hz, 2 H, H(a)), 6.90 (m, 2 H, H(11)), 7.15 (d, br,3JHH
=
8.1 Hz, 1 H, H(5)), 7.36 (m, br, 2 H, H(9)), 7.50 (s, br, 1 H,
H(3)), 7.87 (d, 3JHH = 8.1 Hz, 1 H, H(6)), 9.63 (m, 2 H, 1H(2)).
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{ H} C-NMR (100.6 MHz, CD2Cl2, 298 K): d = −1.4 (C-k),
17.8–19.0 (C-e, C-g, C-h, C-j), 20.7 (10-CH3), 22.1 (C-b, C-f, C-
i), 67.0 (C-a), 84.9 (C-c), 100.4 (C-d), 107.2 (C-3), 118.7 (C-5),
121.2 (C-9), 123.6 (C-6), 125.4 (C-11), 135.8 (C-1), 140.2 (C-2),
151.5 (C-10), 151.8 (C-7/C-8), 152.7 (C-12), 153.6 (C-7/C-8),
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161.9 (C-4). { H} Si-NMR (79.5 MHz, CDCl3, 298 K): d =
−21.9 (≡C–Si), 0.3 ((CH3)3Si–). IR (neat): m [cm−1] = 2953 (s),
2921 (s), 2854 (s), 2180 (vw), 1584 (m), 1469 (m), 1408 (m), 1336
(w), 1259 (s), 1246 (s), 1138 (m), 1096 (s), 1021 (s), 910 (m), 861
(s), 834 (s), 799 (s), 693 (m). MS (FAB): m/z = 1774.9 [M −
Cl]+. C87H172ClN5OPdSi13 (1811.34 g.mol−1): calcd.: C 57.69, H
9.57, N 3.87; found: C 57.99, H 9.97, N 3.42.
General procedure for the preparation of the palladium
complexes 11–14
The BPI-substituted carbosilane (0.05 mmol) was dissolved in
5 ml of CH2Cl2 and 1.5 molar equivalents of triethylamine
per BPI-ligand were added to this solution. Subsequently, 1.5
molar equivalents of [(PhCN)2PdCl2] were added for every
BPI-equivalent and the reaction mixture then stirred at room
temperature for 24 h. After removal of the volatiles in vacuo
the yellow–ochre residue was washed with 3 × 10 ml of water
and 3 × 10 ml of n-hexane. The crude product was taken up
in CH2Cl2, filtered through Celite and the filtrate dried over
MgSO4. After removal of the solvent in vacuo, the product
palladium complex was obtained as an analytically pure yellow
oil (11) or amorphous solid (12–14).
[G-0]4-exo-4-[C≡CCH2CH2O]-10-MeBPIPdCl (13a)
Yield: 14.5 mg (5.65 lmol, 63%), Mp: 88 ◦C. 1H-NMR
(300.17 MHz, CDCl3, 298 K): d = 0.19 (s, 24 H, H(e)), 0.73
(m, 16 H, H(f), H(h)), 1.51 (m, 8 H, H(g)), 2.35 (s, br, 24 H,
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3
10-CH3), 2.78 (t, JHH = 7.4 Hz, 8 H, H(b)), 4.09 (t, JHH
=
7.4 Hz, 8 H, H(a)), 6.75 (m, 8 H, H(11)), 6.86 (m, 4 H, H(5)),
3
7.15–7.19 (m, br, 12 H, H(3), H(9)), 7.67 (d, JHH = 8.1 Hz,
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13
4 H, H(6)), 9.50 (m, 8 H, 1H(2)). { H} C-NMR (100.6 MHz,
CDCl3, 298 K): d = −1.4 (C-e), 17.1/18.7/20.8 (C-f, C-g, C-h),
20.9 (10-CH3), 21.0 (C-b), 66.7 (C-a), 86.3 (C-c), 102.6 (C-d),
107.2 (C-3), 118.8 (C-5), 121.4/121.5 (C-9), 124.4 (C-6), 125.6
(C-11), 126.4 (C-1), 139.0 (C-2), 150.3 (C-10), 151.3/151.4 (C-
4-[tBuSi(CH3)2C≡CCH2CH2O]-10-MeBPIPdCl (11)
Yield: 10.0 mg (19.2 lmol, 65%). Mp: 140 ◦C. 1H-NMR
(300.17 MHz, CDCl3, 298 K): d = 0.11 (s, 6 H, H(e)), 0.95
3
(s, 9 H, H(g)), 2.40 (s, 6 H, 10-CH3), 2.79 (t, JHH = 7.3 Hz,
3
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2 H, H(b)), 4.23 (t, JHH = 7.3 Hz, 2 H, H(a)), 6.85 (m, 2 H,
7/C-8), 152.9 (C-12), 154.1 (C-7/C-8), 161.7 (C-4). { H} Si-
NMR (79.5 MHz, CDCl3, 298 K): d = −17.4 (≡C-Si), 1.2
(–Si(CH3)2–). IR (neat): m [cm−1] = 2950 (w), 2906 (w), 2883
(w), 2174 (w), 1581 (s), 1519 (m), 1470 (s), 1403 (vw), 1364 (w),
1331 (w), 1288 (m), 1231 (m), 1189 (w), 1102 (w), 1085 (w),
1020 (w), 815 (m). MS (FAB): m/z = 2534.5 [M − Cl]+, 1249.4
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4
H(11)), 6.97 (dd, JHH = 8.1 Hz, JHH = 2.5 Hz, 1 H, H(5)),
7.26 (m, 2 H, H(9)), 7.45 (d, 4JHH = 2.5 Hz, 1 H, H(3)), 7.82 (d,
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3JHH = 8.1 Hz, 1 H, H(6)), 9.64 (m, 2 H, 1H(2)). { H} C-NMR
(75.5 MHz, CDCl3, 298 K): d = −4.52 (C-e), 16.3 (C-f), 20.6 (10-
CH3), 20.9 (C-b), 26.1 (C-g), 66.7 (C-a), 92.7 (C-c), 105.7 (C-d),
D a l t o n T r a n s . , 2 0 0 5 , 1 4 0 3 – 1 4 1 5
1 4 1 3