Iron-Centered Metallodendrimers
171 176
113.69 (CH, Ar), 67.28 (CH2O), 44.84 (ClCH2), 42.55 (Cq CH2), 41.83 (CH2),
32.25 (CH2), 28.55 (CH2), 23.51 (CH2); elemental analysis calcd (%) for
C21H29OCl (332.91): C 75.76, H 8.78; found: C 75.14, H 8.50.
200 MHz): d 7.20 (d, 3J(H,H) 8.0 Hz, 10H; Ar), 6.82 (d, 3J(H,H)
8.0 Hz, 10H; Ar), 5.54 (m, 9H; CH2 CH), 5.00 (m, 18H; CH2 CH), 4.61
(s, 2H; HOCH2), 3.98 (t, 3J(H,H) 6.4 Hz, 4H; CH2O), 3.87 (t, 3J(H,H)
3
À
6.4 Hz, 6H; CH2O), 2.41 (d, J(H,H) 7.2 Hz, 18H; CH2 CH CH2), 1.85
(m, 10H; CH2), 1.60 (m, 8H; CH2); 13C NMR (CDCl3, 50.33 MHz): d
158.90 (Cq, ArO), 156.81 (Cq, ArO), 156.72 (Cq, ArO), 138.24 (Cq, Ar),
137.42 (Cq, Ar), 134.57 (CH2CH), 128.55 (CH, Ar), 127.49 (CH, Ar), 127.38
(CH, Ar), 117.37 (CHCH2), 114.45 (CH, Ar), 113.91 (CH, Ar), 113.70 (CH,
Ar), 68.09 (CH2O), 67.72 (CH2O), 67.50 (CH2O), 65.00 (HOCH2), 42.54
(Cq CH2), 41.95 (CH2), 33.65 (CH2), 29.02 (CH2), 28.93 (CH2), 23.64 (CH2),
Chloroalkyl 9-allyl dendron 8: This compound was synthesized according
the same procedure described above for 3, by using 7 (72 h). Dendron 8 was
obtained in 72% yield after chromatography. 1H NMR (CDCl3, 200 MHz):
d 7.22 (d, 3J(H,H) 8.8 Hz, 8H; Ar), 6.89 (d, 3J(H,H) 8.8 Hz, 8H; Ar),
3
5.58 (m, 9H; CH2 CH), 5.05 (m, 18H; CH2 CH), 3.97 (t, J(H,H) 7.0 Hz,
2H; CH2O), 3.89 (t, 3J(H,H) 8.0 Hz, 8H; CH2O), 3.57 (t, 3J(H,H)
3
À
8.0 Hz, 2H; CH2Cl), 2.41 (d, J(H,H) 7.2 Hz, 6H; CH2 CH CH2), 1.83
(m, 8H; CH2), 1.62 (m, 10H; CH2); 13C NMR (CDCl3, 50.33 MHz): d
156.87 (Cq, ArO), 138.30 (Cq, Ar), 137.56 (Cq, Ar), 134.70 (CH2CH), 127.62
(CH, Ar), 117.50 (CHCH2), 113.84 (CH, Ar), 68.22 (CH2O), 67.90 (CH2O),
44.95 (ClCH2), 42.68 (Cq CH2), 41.97 (CH2), 33.79 (CH2), 32.39 (CH2), 28.69
(CH2), 23.78 (CH2), 23.64 (CH2); MALDI TOFmass spectrum: m/z:
22. 67 (CH2); MALDI TOFmass spectrum: m/z: 1127.55 [MNa] (calcd
1128.58); elemental analysis calcd (%) for C76H96O6 (1105.57): C 82.56, H
8.75; found: C 82.82, H 8.75.
Bromobenzyl 3-allyl dendron 6: PBr3 (0.086 g, 0.317 mmol) was added to a
cooled mixture (08C) of dendron 5 (0.400 g, 0.951 mmol) in toluene
(10 mL). The resulting solution was stirred at room temperature for 4 h.
After removal of the solvent, the residue was extracted with Et2O, washed
with water, and dried over sodium sulfate. The solvent was removed under
1040.73 [MNa] (calcd 1040.92); elemental analysis calcd (%) for
C69H89O4Cl (1017.92): C 81.42, H 8.81; found : C 80.52, H 8.65.
Iodoalkyl 3-allyl dendron 4: A mixture of 3 (1.314 g, 3.958 mmol) and NaI
(2.968 g, 19.787 mmol) in butanone (30 mL) was stirred for 24 h at 808C.
After removal of the solvent under vacuum, the residue was extracted with
Et2O (3 Â 20 mL). The resulting solution washed with and an aqueous
solution saturated with Na2S2O3, dried over sodium sulfate and then
filtered. The solvent was removed under vacuum to provide 4 as a colorless
oil (1.580 g, 94%). 1H NMR (CDCl3, 200 MHz): d 7.26 (d, 3J(H,H)
8.8 Hz, 2H; Ar), 6.85 (d, 3J(H,H) 8.8 Hz, 2H; Ar), 5.56 (m, 3H;
1
vacuum providing 6 as a yellow oil (0.377 g, 0.779 mmol, 82%). H NMR
(CDCl3, 200 MHz): d 7.24 (d, 3J(H,H) 8.0 Hz, 4H; Ar), 6.85 (d,
3J(H,H) 8.0 Hz, 4H; Ar), 5.50 (m, 3H; CH2 CH), 5.03 (m, 6H;
CH2 CH), 4.50 (s, 2H; BrCH2), 3.98 (t, 3J(H,H) 6.2 Hz, 2H; CH2O),
3.97 (t, 3J(H,H) 6.2 Hz, 2H; CH2O), 2.43 (d, 3J(H,H) 7.2 Hz, 6H;
CH2 CH CH2), 1.86 (m, 4H; CH2 CH2), 1.66 (m, 2H; CH2); 13C NMR
(CDCl3, 50.33 MHz): d 159.20 (Cq, ArO), 156 .83 (Cq, ArO), 137.83 (Cq,
Ar), 134.57 (CHCH2), 130.33 (Cq, Ar), 127.53 (CH, Ar), 117.40 (CH, Ar),
114.62 (CH, Ar), 113.72 (CH, Ar), 67.72 (CH2O), 67.43 (CH2O), 42.76
(Cq CH2), 41.84 (CH2), 34.00 (BrCH2), 29.01 (CH2), 22.67 (CH2); elemental
analysis calcd (%) for C28H35O2Br (483.48): C 69.55, H 7.29; found: C 69.58,
H 7.61.
À
À
CH2 CH), 5.03 (m, 6H; CH2 CH), 3.96 (t, 3J(H,H) 6.2 Hz, 2H;
CH2O), 3.21 (t, 3J(H,H) 7.0 Hz, 2H; CH2I), 2.42 (d, 3J(H,H) 7.2 Hz,
À
À
6H; CH2 CH CH2), 1.85 (m, 4H; CH2 CH2), 1.57 (m, 2H; CH2);
13C NMR (CDCl3, 50.33 MHz): d 156.67 (Cq, ArO), 137. 54 (Cq, Ar),
134.55 (Cq, Ar), 127.53 (Cq, Ar), 117.44 (CH, Ar), 113.69 (CH, Ar), 67.24
(CH2O), 42.55 (Cq CH2), 41.83 (CH2), 33.13 (CH2), 28.20 (CH2), 27.12
(CH2), 6.73 (ICH2); elemental analysis calcd (%) for C21H29OI (424.36): C
59.44, H 6.89; found : C 59.47, H 6.8.
Bromobenzyl 9-allyl dendron 13: This compound was prepared according
to the same procedure as described above for 6, but with 12 instead of 5;
this gave a 95% yield after chromatography. 1H NMR (CDCl3, 200 MHz):
d 7.22 (m, 10H; Ar), 6.82 (m, 10H; Ar), 5.53 (m, 9H; CH2 CH), 5.01 (m,
Iodoalkyl 9-allyl dendron 11: Compound 11 was synthesized according to
the same procedure decscribed above for 4, but with 8 instead of 3. Yellow
18H; CH2 CH), 4.50 (s, 2H; BrCH2), 4.00 (t, 3J(H,H) 6.4 Hz, 4H;
CH2O), 3.89 (t, 3J(H,H) 6.4 Hz, 6H; CH2O), 2.42 (d, 3J(H,H) 7.2 Hz,
oil, 91% yield. 1H NMR (CDCl3, 200 MHz): d 7.20 (d, 3J(H,H) 8.8 Hz,
18H; CH2 CH CH2), 1.86 (m, 10H; CH2), 1.63 (m, 8H; CH2); 13C NMR
(CDCl3, 50.33 MHz): d 157.31 (Cq, ArO), 157.23 (Cq, ArO), 138. 74 (Cq,
Ar), 137. 93 (Cq, Ar), 135.06 (CH2CH), 130.81 (CH, Ar), 130.16 (CH, Ar),
127.98 (CH, Ar), 127.87 (CH, Ar), 117.87 (CHCH2), 115.13 (CH, Ar),
114.41 (CH, Ar), 114.20 (CH, Ar), 68.59 (CH2O), 60.23 (CH2O), 67.96
À
3
8H; Ar), 6.81 (d, J(H,H) 8.8 Hz, 8H; Ar), 5.53 (m, 9H; CH2 CH), 5.00
(m, 18H; CH2 CH), 3.96 (t, 3J(H,H) 8.0 Hz, 2H; CH2O), 3.90 (t,
3J(H,H) 8.0 Hz, 6H; CH2O), 3.24 (t, 3J(H,H) 8.0 Hz, 2H; CH2Cl), 2.41
3
À
(d, J(H,H) 7.0 Hz, 6H; CH2 CH CH2), 1.83 (m, 8H; CH2), 1.60 (m,
10H; CH2); 13C NMR (CDCl3, 50.33 MHz): d 156.71 (Cq, ArO), 138.30
À
(CH2O), 43.04 (Cq CH2), 42.45 (CH2), 34.47 (CH2), 34.15 (BrCH2), 30.09
(Cq, Ar), 137.42 (Cq, Ar), 134.57 (CH2 CH), 127.45 (CH, Ar), 117.39
(CH2), 29.50 (CH2), 29.38 (CH2), 24.14 (CH2), 23.16 (CH2), MALDI TOF
(CH CH2), 113.88 (CH, Ar), 113.68 (CH, Ar), 68.06 (CH2O), 67.28
(CH2O), 42.54 (Cq CH2), 41.95 (CH2), 33.64 (CH2), 32.13 (CH2), 28.20
(CH2), 27.12 (CH2), 23.62 (CH2), 6.71 (ICH2); MALDI TOFmass
mass spectrum: m/z: 1191.62 [MNa] (calcd 1191.48); elemental analysis
calcd (%) for C76H95O5Br (1168.49): C 78.12, H 8.19; found : C 77.29,
H 8.36.
spectrum: m/z: 1132.43 [MNa] (calcd 1132.35); elemental analysis calcd
18-Allyl dendrimer 10: A mixture of 1 (0.025 g, 0.058 mmol), KOH
(0.059 g, 1.050 mmol), and 4 (0.370 g, 0.872 mmol) in dimethoxyethane
(10 mL) was stirred for 24 h at 608C. After removal of the solvent under
vacuum, the residue was extracted with pentane (3 Â 10 mL), and the
resulting solution was concentrated and purified by chromatography on a
silica-gel column with a 4:1 pentane/diethyl ether mixture providing 10 as a
yellow-orange oil (0.052 g, 0.0235 mmol, 40%). 1H NMR (CDCl3,
200 MHz): d 7.22 (d, 3J(H,H) 8.0 Hz, 12H; Ar), 6.85 (d, 3J(H,H)
(%) for C69H89O4I (1109.38): C 74.71, H 8.09; found : C 74.91, H 8.04.
Benzylalcohol 3-allyl dendron 5:
A mixture of HOCH2-p-C6H4OH
(0.146 g, 1.176 mmol) and K2CO3 (0.163g, 1.18 mmol) in DMF(5 mL)
was stirred for 30 min at room temperature. Dendron 4 (0.500g, 1.18 mmol)
was then added to the reaction mixture, and the resulting solution stirred at
408C for 72 h. The mixture was extracted with CH2Cl2 (3 Â 20 mL), and the
resulting solution washed with water and dried over sodium sulfate. After
removal of the solvent under vacuum, the product was purified by
chromatography on a silica-gel column with a 7:3 pentane/diethyl ether
8.0 Hz, 12H; Ar), 5.54 (m, 18H; CH2 CH), 5.03 (m, 36H; CH2 CH),
4.62 (s, 5H; C5H5), 3.96 (m, 12H; CH2O), 2.85 (br, 12H; CH2Ar), 2.4 (d,
1
3
mixture to provide 5 as a yellow oil (0.248 g, 0.590 mmol, 50%). H NMR
À
J(H,H) 7.0 Hz, 36H; CH2 CH CH2), 1.85 (m, 4H; CH2), 1.66 (m, CH2);
(CDCl3, 200 MHz): d 7.24 (d, 3J(H,H) 8.0 Hz, 4H; Ar), 6.85 (d,
13C NMR (CDCl3, 50.33 MHz): d 156.91 (Cq, ArO), 137.54 (Cq, Ar),
3J(H,H) 8.0 Hz, 4H; Ar), 5.50 (m, 3H; CH2 CH), 5.03 (m, 6H;
134.66 (CH2 CH), 127.68 (CHAr), 117.51 (CH2 CH), 113.87 (CHAr), 102.44
(Cq, Ar), 77.97 (C5H5), 67.59 (CH2O), 42.69 (Cq CH2), 41.98 (CH2), 31.80
(CH2), 29.36 (CH2), 26.00 (CH2); MALDI TOFmass spectrum: m/z:
CH2 CH), 4.62 (brs, 2H; HOCH2), 3.98 (t, 3J(H,H) 6.2 Hz, 2H;
CH2O), 3.97 (t, 3J(H,H) 6.4 Hz, 2H; CH2O), 2.44 (d, 3J(H,H) 7.2 Hz,
6H; CH2 CH CH2), 1.86 (m, 4H; CH2 CH2), 1.62 (m, 2H, CH2); 13C NMR
(CDCl3, 50.33 MHz): d 158.90 (Cq, ArO), 156 .83 (Cq, ArO), 137. 83 (Cq,
Ar), 134.68 (CHCH2), 132.96 (Cq, Ar), 128.92 (CH, Ar), 127.69 (CH, Ar),
117.53 (CHCH2), 114.77 (CH, Ar), 114.00 (CH, Ar), 67.92 (CH2O), 67.67
(CH2O), 65.15 (CH2OH), 42.76 (Cq CH2), 40.00 (CH2), 29.13 (CH2), 29.07
(CH2), 22.86 (CH2); elemental analysis calcd (%) for C28H36O3 (420.58): C
79.96, H 8.62; found: C 79.95, H 8.67.
À
À
2061.64 [M À PF6] (calcd 2061.93); elemental analysis calcd (%) for
C143H191O6F6PFe (2206.89): C 77.83, H 8.72; found: C 76.70, H 8.20.
18-Allyl dendrimer 9: Dendrimer 9 was synthesized according to the same
procedure described above for 10, but with 6 instead of 4 (608C, 24 h); this
gave a 50% yield after chromatography. 1H NMR (CDCl3, 200 MHz): d
7.26 (m, 24H; Ar), 6.89 (m, 24H; Ar), 5.56 (m, 18H; CH2 CH), 5.03 (m,
36H; CH2 CH), 4.87 (s, 5H; C5H5), 3.97 (m, 24H; CH2O), 3.10 (br;
3
À
Benzyl alcohol 9-allyl dendron 12: Dendron 12 was synthesized according
to the same procedure as described above for 5, but with 11 instead of 4
(96 h) giving a 90% yield after chromatography. 1H NMR (CDCl3,
CH2Ar), 2.43 (d, J(H,H) 7.0 Hz, 36H; CH2 CH CH2), 1.87 (m, 4H;
CH2), 1.66 (m; CH2); 13C NMR (CDCl3, 50.33 MHz): d 158.06 (Cq, ArO),
156.77 (Cq, ArO), 134.56 (CH2 CH), 128.91 (Cq, Ar), 127.52 (CHAr), 117.39
Chem. Eur. J. 2002, 8, No. 1
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0801-0175 $ 17.50+.50/0
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