M. Yamamura et al. / Journal of Organometallic Chemistry 692 (2007) 313–325
321
3
7.0 Hz, 9H), 2.26 (s, 3H), 3.84 (q, J = 7.0 Hz, 6H), 7.34
4.3. Synthesis of (E)-allyldimethyl[2-(phenylazo)-
phenyl]silane ((E)-5e)
3
4
3
(dd, J = 7.5 Hz, J = 1.5 Hz, 1H), 7.45 (tt, J = 7.5 Hz,
4J = 1.5 Hz, 1H), 7.51 (t, 3J = 7.5 Hz, 2H), 7.74 (d,
3J = 7.5 Hz, 1H), 7.80 (d, 4J = 1.5 Hz, 1H), 7.99 (d,
3J = 7.5 Hz, 2H); 13C{1H} NMR (126 MHz, CDCl3) d
18.12 (CH3), 21.47 (CH3), 58.57 (OCH2), 114.69 (CH),
123.23 (CH), 128.98 (CH), 130.71 (CH), 132.12 (CH),
132.84 (CSi), 137.88 (CH), 140.66 (CMe), 152.60 (CN),
155.48 (CN); 29Si NMR (99 MHz, CDCl3) d 59.07 (s). Anal.
Calc. for C19H26N2O3Si: C, 63.65; H, 7.31; N, 7.81. Found:
C, 63.59; H, 7.26; N, 7.71. (E)-5b: red oil; 1H NMR
Similarly to the synthesis of (E)-5a–d, (E)-5e was synthe-
sized from 2-iodoazobenzene (500 mg, 1.62 mmol) and
allylchlorodimethylsilane (0.30 mL, 2.05 mmol). Separa-
tion with HPLC gave a red oil of (E)-allyldimethyl[2-
(phenylazo)phenyl]silane ((E)-5e) (332 mg, 73%). (E)-5e:
1
red oil; H NMR (500 MHz, CDCl3) d 0.38 (s, 6H), 1.92
3
3
(d, J = 7.0 Hz, 2H), 4.79 (d, J = 10.5 Hz, 1H), 4.83 (d,
3J = 15.0 Hz, 1H), 5.77 (ddt, J = 15.0 Hz, J = 10.5 Hz,
3
3
3
3
4
(500 MHz, CDCl3) d 1.20 (t, J = 7.0 Hz, 6H), 1.46 (dd,
3J = 7.0 Hz, 1H), 7.43 (td, J = 7.5 Hz, J = 1.5 Hz, 1H),
7.50 (t, 3J = 7.5 Hz, 2H), 7.67 (dd, 3J = 7.5 Hz,
4J = 1.5 Hz, 1H), 7.74 (t, 3J = 7.5 Hz, 2H), 7.75 (dd,
3J = 7.5 Hz, J = 1.5 Hz, 3H), 1.90 (d, J = 7.5 Hz, 2H),
4
3
3
2.40 (s, 3H), 3.77–3.93 (m, 4H), 5.20 (qd, J = 15.0 Hz,
3J = 7.5 Hz, 1H), 5.32 (qtd, 3J = 15.0 Hz, 3J = 7.5 Hz,
3J = 7.5 Hz, J = 1.5 Hz, 1H), 7.92 (d, J = 7.5 Hz, 2H);
13C NMR (126 MHz, CDCl3) d ꢁ1.68 (CH3), 24.82
(CH2), 113.17 (CH2), 114.69 (CH), 123.12 (CH), 129.08
(CH), 130.03 (CH), 130.05 (CH), 130.91 (CH), 134.95
(CH), 134.96 (CH), 140.13 (CSi), 152.33 (CN), 157.22
(CN); 29Si NMR (99 MHz, CDCl3) d ꢁ4.26 (s). Anal. Calc.
for C17H20N2Si: C, 72.81; H, 7.19; N, 9.99. Found: C,
72.77; H, 7.30; N, 9.71%.
4
3
4J = 1.5 Hz, 1H), 7.34 (td, J = 7.5 Hz, J = 1.5 Hz, 1H),
3
4
3
3
7.46 (t, J = 7.5 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H), 7.76
(d, 3J = 7.5 Hz, 1H), 7.79 (t, 4J = 1.5 Hz, 1H), 7.98 (d,
3J = 7.5 Hz, 2H); 13C{1H} NMR (126 MHz, CDCl3) d
17.97 (CH3), 18.25 (CH3), 20.94 (CH@CHCH2), 58.69
(OCH2), 114.69 (CH), 123.18 (CH), 124.79 (CH), 124.90
(CH), 129.05 (CH), 130.68 (CH), 131.80 (CH), 135.15
(CSi), 137.20 (CH), 140.59 (CMe), 152.57 (CN), 155.73
(CN); 29Si NMR (99 MHz, CDCl3) d ꢁ24.55 (s). Anal.
Calc. for C21H28N2O2Si: C, 68.44; H, 7.66; N, 7.60. Found:
C, 68.38; H, 7.69; N, 7.40%. (E)-5c: red oil; 1H NMR
(500 MHz, CDCl3) d 1.20 (t, 3J = 7.0 Hz, 3H), 1.27 (t,
3J = 7.0 Hz, 3H), 1.40–1.47 (m, 1H), 1.64–1.76 (m, 3H),
1.93–1.98 (m, 2H), 2.15–2.21 (m, 1H), 3.84–3.87 (m, 2H),
3.91–3.98 (m, 2H), 5.58–5.63 (m, 1H), 5.87–5.92 (m, 1H),
7.47–7.57 (m, 5H), 7.85 (d, 3J = 7.5 Hz, 1H), 8.02 (d,
3J = 7.8 Hz, 2H), 8.06 (d, 3J = 7.5 Hz, 1H); 13C{1H}
NMR (126 MHz, CDCl3) d 8.28 (CH3), 18.41 (CH3),
22.27 (CH2), 22.90 (CH2), 25.02 (CH2), 26.24 (CH), 58.89
(OCH2), 59.02 (OCH2), 114.55 (CH), 123.42 (CH), 125.68
(CH), 126.91 (CH), 129.13 (CH), 130.92 (CH), 131.01
(CH), 131.04 (CH), 135.12 (CSi), 137.23 (CH), 152.58
(CN), 157.31 (CN); 29Si NMR (99 MHz, CDCl3) d
ꢁ24.53 (s); UV/Vis (CHCl3) kmax (e) 324 (1.9 · 04),
448 nm (1.0 · 04). Anal. Calc. for C22H28N2O2Si: C,
69.43; H, 7.42; N, 7.36. Found: C, 69.44; H, 7.45; N,
4.4. Synthesis of (E)-allyldifluoro[2-(phenylazo)-
phenyl]silane ((E)-7a–d)
To an ethereal solution of (E)-5a (81.5 mg, 0.240 mmol)
was added BF3 Æ Et2O (25 lL, 0.20 mmol) and the reaction
mixture was stirred at room temperature for 20 h. Removal
of the solvent, addition of hexane, filtration of the insoluble
materials and evaporation of the solvent gave a yellow vis-
cous oil. Recrystallization of the oil from hexane gave yel-
low crystals of (E)-allyldifluoro[2-(phenylazo)phenyl]silane
((E)-7a) (13.8 mg, 63%). (E)-7a: yellow crystals (hexane);
1
m.p. 38 ꢁC; H NMR (500 MHz, CDCl3) d 1.87–1.94 (m,
2H), 4.72 (d, 3J = 17.0 Hz, 1H), 4.76 (d, 3J = 10.2 Hz,
1H), 5.57 (ddt, 3J = 17.0 Hz, 3J = 10.2 Hz, 3J = 7.5 Hz,
1H), 7.53–7.64 (m, 4H), 7.73 (dt, 3J = 7.6 Hz,
3
4
4J = 1.6 Hz, 1H), 7.94 (dd, J = 7.3 Hz, J = 1.6 Hz, 1H),
8.04–8.07 (m, 2H), 8.14 (d, 3J = 7.0 Hz, 1H); 13C{1H}
NMR (126 MHz, CDCl3) d 22.92 (t, JC–F = 16.2 Hz,
2
1
2
7.12%. (E)-5d: red oil; H NMR (500 MHz, CDCl3) d 1.21
CH2), 116.07 (s, CH2), 120.00 (t, JC–F = 18.0 Hz, CSi),
(t, J = 7.5 Hz, 3H), 2.19 (dd, J = 13.0 Hz, J = 8.0 Hz,
1H), 2.29 (dd, J = 13.0 Hz, J = 8.0 Hz, 1H), 3.80 (q,
J = 7.5 Hz, 2H), 4.76 (d, J = 10.7 Hz, 1H), 4.82 (d,
J = 16.7 Hz, 1H), 5.77 (ddt, J = 16.7 Hz, J = 10.7 Hz,
J = 8.0 Hz, 1H), 7.26–7.32 (m, 4H), 7.33–7.35 (m, 2H),
7.45–7.49 (m, 3H), 7.52–7.56 (m, 3H), 7.82 (d, J = 8.0 Hz,
1H), 7.94 (d, J = 7.5 Hz, 1H); 13C{1H} NMR (126 MHz,
CDCl3) d 8.31 (CH3), 23.42 (CH2), 59.34 (CH2), 114.36
(CH2), 116.08 (CH), 122.97 (CH), 127.54 (CH), 128.79
(CH), 129.35 (CH), 130.38 (CH), 130.75 (CH), 131.07
(CH), 131.90 (CH), 133.62 (CH), 135.66 (CSi), 136.17
(CSi), 136.55 (CH), 152.21 (CN), 156.87 (CN); 29Si NMR
123.12 (s, CH), 129.47 (s, CH), 129.52 (s, CH), 130.71 (s,
CH), 132.11 (s, CH), 132.32 (s, CH), 132.90 (s, CH),
3
3
137.21 (t, JC–F = 2.5 Hz), 149.11 (s, CN), 156.43 (t, JC–
F = 3.1 Hz, CN); 19F NMR (254 MHz, CDCl3, r.t.) d
1
140.42 (s, JSi–F = 278 Hz); 19F NMR (254 MHz, CD2Cl2,
ꢁ90 ꢁC) d ꢁ141.27 (br), ꢁ127.17 (br); 29Si NMR (99 MHz,
1
CDCl3) d ꢁ38.53 (t, JSi–F = 277.6 Hz). Anal. Calc. for
C15H14F2N2Si: C, 62.48; H, 4.89; N, 9.71. Found: C,
62.24; H, 5.04; N, 9.62%. (E)-7b: yellow oil; 1H NMR
3
(500 MHz, CDCl3) d 1.46 (dd, J = 7.7 Hz, 4J = 1.5 Hz,
3H), 1.78–1.81 (m, 2H), 2.47 (s, 3H), 5.12 (dq,
3J = 15.0 Hz, 3J = 7.7 Hz, 1H), 5.55 (dtq, 3J = 15.0 Hz,
4
(99 MHz, CDCl3)
d
ꢁ8.25 (s). Anal. Calc. for
3J = 7.5 Hz, J = 1.5 Hz, 1H), 7.52–7.56 (m, 4H), 7.77 (s,
3
C23H24N2OSi: C, 74.15; H, 6.49; N, 7.52. Found: C,
74.06; H, 6.76; N, 7.30%.
1H), 8.02 (d, J = 8.0 Hz, 3H); 13C{1H} NMR (126 MHz,
2
CDCl3) d 17.96 (s, CH3), 21.19 (t, JC–F = 15.3 Hz, CH2),