L. Dosta´l et al. / Journal of Organometallic Chemistry 691 (2006) 35–44
37
11.43%. 1H NMR (C6D6): 0.28 (4H, d, CH2–iBu), 1.22
(12H, d, CH3–iBu), 2.06 (2H, m, CH–iBu), 2.21 (12H, s,
(CH3)2N), 3.42 (4H, s, NCH2), 6.99 (2H, d, Ar–H3,5),
7.22 (1H, t, Ar–H4). 13C NMR (C6D6): 21.62 (CH2–iBu),
23.85 (CH–iBu), 29.37 (CH3–iBu), 45.85 ((CH3)2N), 67.80
(NCH2), 124.24 (Ar–C3,5), 127.78 (Ar–C4), 146.64 (Ar–
C2,6), (Ar–C1) not found. 27Al NMR (C6D6): 156.3
(m1/2 = 7.9 kHz).
ing of the solvent yielded 5 as pale yellow oil (in some cases
traces of free ligand 1,3-(MeOCH2)2C6H4 was removed un-
der high vacuo) 0.33 g, 56%. Anal. Calc. for C13H22O2Sn:
C, 47.46; H, 6.74. Found: C, 47.51; H, 6.92%.
1
MW = 330. MS: m/z 315, 100% [M ꢀ CH3]+. H NMR
(C6D6): 0.55 (9H, s, (CH3)3Sn, 2J(119Sn, 1H) = 54 Hz),
3.10 (6H, s, CH3O), 4.42 (4H, s, OCH2), 7.23 (1H, t, Ar–
H4), 7.36 (2H, d, Ar–H3,5). 13C NMR (C6D6): ꢀ4.47
1
((CH3)3Sn, J(119Sn, 13C) = 353 Hz), 57.29 (CH3O), 76.66
(OCH2, 1J(119Sn, 13C) = 21.6 Hz), 126.73 (br, Ar–C3,5),
127.28 (br, Ar–C4), 142.31 (Ar–C1), 146.73 (Ar–C2,6,
nJ(119Sn, 13C) = 28.0 Hz). 119Sn NMR (C6D6): ꢀ50.5.
2.3. Reactions of 1–3 with Ph3SnOH
2.3.1. Preparation of 2,6-(MeOCH2)2C6H3SnPh3 (4)
Ph3SnOH (0.48 g, 1.3 mmol) was added in one portion
to a solution of 1 (0.4 g, 1.3 mmol) in hexane (50 ml) and
resulting suspension was stirred for additional 24 h at room
temperature. The reaction mixture was exposed to air for
12 h and the insoluble material was filtered off. Evaporat-
ing of the solvent yielded 4 as white crystals (in some cases
recrystalization from hexane to remove traces of Ph3SnOH
or free ligand 1,3-(MeOCH2)2C6H4 was necessary) 0.31 g,
45%, m.p. 88–93 ꢁC. Anal. Calc. for C28H28O2Sn: C,
66.27; H, 5.48. Found: C, 66.12; H, 5.62%. MW = 516.
MS: m/z 477, [M + K ꢀ C6H6]+; m/z 461, [M + Na ꢀ
C6H6]+; m/z 439, 100% [M–C6H5]+. 1H NMR (C6D6):
2.58 (6H, s, CH3O), 4.08 (4H, s, OCH2), 7.13–7.58 (18H,
complex pattern, SnPh3, SnC6H3-ligand). 119Sn NMR
(C6D6): ꢀ162.5.
2.4.2. Preparation of 2,6(tBuOCH2)2C6H3SnMe3 (7)
Similar to procedure as for 5: Me3SnOH (0.2 g,
1.1 mmol); 2 (0.43 g, 1.1 mmol) yielded colourless oil 7
0.24 g, 52%. Anal. Calc. for C19H34O2Sn: C, 55.23; H,
8.29. Found: C, 55.62; H, 8.37%. MW = 414. MS: m/z
437, [M + Na]+; m/z 453, 100% [M + K]+; m/z 399,
[M ꢀ CH3]+. 1H NMR (C6D6): 0.47 (9H, s, (CH3)3Sn,
2J(119Sn, 1H) = 54 Hz), 1.15 (18H, s, (CH3)3CO), 4.43 (4H,
s, OCH2), 7.24 (1H, t, Ar–H4), 7.43 (2H, d, Ar–H3,5). 13C
1
NMR (C6D6): ꢀ4.00 ((CH3)3Sn, J(119Sn, 13C) = 347 Hz),
28.12 ((CH3)3CO), 67.10 (OCH2, nJ(119Sn, 13C) = 29.6
Hz), 73.87 ((CH3)3CO), 127.45 (Ar–C3,5, nJ(119Sn,
13C) = 41 Hz), 128.95 (Ar–C4, nJ(119Sn, 13C) = 9 Hz),
140.32 (Ar–C1, 1J(119Sn, 13C) = 470 Hz), 147.96 (Ar–C2,6,
nJ(119Sn, 13C) = 28.0 Hz). 119Sn NMR (C6D6): ꢀ53.8.
2.3.2. Preparation of 2,6-(tBuOCH2)2C6H3SnPh3 (6)
Similar to procedure as for 4: Ph3SnOH (0.44 g,
1.2 mmol); 2 (0.47 g, 1.2 mmol) yielded white crystals of 6
0.38 g, 53%, m.p. 155–157 ꢁC. Anal. Calc. for C34H40O2Sn:
C, 68.13; H, 6.73. Found: C, 68.26; H, 6.90%. MW = 600.
2.4.3. Preparation of 2,6-(Me2NCH2)2C6H3SnMe (9)
3
Similar to procedure as for 5: Me3SnOH (0.31 g,
1.7 mmol); 3 (0.57 g, 1.7 mmol), 48 h, yielded colourless
oil 9 0.3 g, 49%. Anal. Calc. for C15H28N2Sn: C, 50.74;
H, 7.95. Found: C, 51.01; H, 8.05%. MW = 356. MS: m/
1
MS: m/z 639, [M + K]+; m/z 623, 100% [M + Na]+. H
1
z 341, 100% [M ꢀ CH3]+. H NMR (C6D6): 0.37 (9H, s,
NMR (C6D6): 0.85 (18H, s, (CH3)3CO), 4.38 (4H, s,
OCH2), 7.31–7.67 (18H, complex pattern, SnPh3,
SnC6H3-ligand). 119Sn NMR (C6D6): ꢀ153.0.
(CH3)3Sn, 2J(119Sn, 1H) = 53 Hz), 2.20 (12H, s,
(CH3)2N), 3.60 (4H, s, NCH2), 7.26 (3H, m, Ar–H3,4,5).
119Sn NMR (C6D6): ꢀ85.9.
2.5. Reactions of 1 and 2 with (nBu3Sn)2O
2.3.3. Preparation of 2,6-(Me2NCH2)2C6H3SnPh (8)
3
Similar to procedure as for 4: Ph3SnOH (0.46 g,
1.26 mmol); 3 (0.42 g, 1.26 mmol), 48 h, yielded white crys-
tals of 8 0.28 g, 41%, m.p. 85–90 ꢁC. Anal. Calc. for
C30H34N2Sn: C, 66.57; H, 6.33. Found: C, 66.36; H,
2.5.1. Reaction of 1 with (nBu3Sn)2O
Solution of 1 (0.55 g, 1.79 mmol) in hexane (50 ml)
was added to neat (nBu3Sn)2O (1.1 g, 1.79 mmol) and
was stirred for additional 24 h at room temperature.
The reaction mixture was exposed to air for 12 h and
the insoluble material was filtered off. Evaporating
of the solvent yielded mixture of nBu3SniBu and 2,6-
(MeOCH2)2C6H3SnnBu3 (10). 1H NMR (C6D6): 0.95–
1
6.52%. MW = 542. MS: m/z 465, 100% [M ꢀ C6H5]+. H
NMR (C6D6): 2.18 (12H, s, (CH3)2N), 3.30 (4H, s,
NCH2), 7.08–7.60 (18H, complex pattern, SnPh3,
SnC6H3-ligand). 119Sn NMR (C6D6): ꢀ201.7.
n
2.05 (complex pattern: Bu3-SniBu and 10-SnnBu3), 3.17
2.4. Reactions of 1–3 with Me3SnOH
(6H, s, CH3O), 4.45 (4H, s, OCH2), 7.20–7.25 (3H, m,
Ar–H3,4,5). 119Sn NMR (C6D6): ꢀ51.5 (10), ꢀ17.3
nBu3SniBu (ratio 1:1).
2.4.1. Preparation of 2,6-(MeOCH2)2C6H3SnMe3 (5)
Me3SnOH (0.32 g, 1.79 mmol) was added in one portion
to a solution of 1 (0.55 g, 1.79 mmol) in hexane (50 ml) and
resulting suspension was stirred for additional 24 h at room
temperature. The reaction mixture was exposed to air for
12 h and the insoluble material was filtered off. Evaporat-
2.5.2. Reaction of 2 with (nBu3Sn)2O
Similar to procedure to 2.5.1: 2 (0.75 g, 1.91 mmol);
(nBu3Sn)2O (1.14 g, 1.91 mmol) yielded mixture of