M.H. Chisholm et al. / Polyhedron 26 (2007) 4436–4444
4439
C18H22F2O2Sn (427.073): C, 50.62; H, 5.19. Found: C,
50.34; H, 5.08%.
13C NMR (C6D6, 100.6 MHz): d 161.6 (C-OCH3), 138.3
(m-CH), 128.3 (ipso-C–Sn), 115.1 (o-CH), 54.5 (C–
OCH3), 43.9 (N(CH3)2) ppm; 118Sn NMR (C6D6,
149.2 MHz): d ꢀ7.4 ppm.
2.3.4. (p-FC6H4)2Sn(NMe2)2
1H NMR (C6D6, 250 MHz): d 7.35 (dd, 3JH–H = 8.5 Hz,
3JH–F = 6.3 Hz m-CH aryl, 4 H), 6.88 (dd, 3JH–H = 8.5 Hz,
2.3.10. (p-Me2NC6H4)3SnOiPr
4JH–F = 8.6 Hz o-CH aryl, 4 H), 2.84 (s, N(CH3)2, 12 H)
(p-Me2NC6H4)2SnCl2 (858 mg, 1.99 mmol) and LiNMe2
1
ppm; 13C NMR (C6D6, 62.9 MHz): d 164.6 (d, JC–F
=
(224 mg, 4.39 mmol). Yield 170 mg, 32%. M.p. 125–126 ꢁC
3
3
245 Hz, C–F), 138.7 (d, JC–F = 7.1 Hz, m-CH), 132.7 (d,
(dec.); 1H NMR (C6D6, 250 MHz): d 7.86 (d, JH–H
=
4JC–F = 4.4 Hz, ipso-C–Sn), 116.4 (d, JC–F = 19.7 Hz,
8.4 Hz, m-CH aryl, 6 H), 6.68 (d, JH–H = 8.4 Hz, o-CH
aryl, 6 H), 4.59 (sept, JH–H = 6 Hz, OCH(CH3)2, 1 H),
2.48 (s, N(CH3)2, 18 H), 1.48 (d, JH–H = 6 Hz,
2
3
3
o-CH), 43.6 (N(CH3)2) ppm.
3
2.3.5. Ph2Sn(OiPr)2
OCH(CH3)2, 6 H) ppm; 13C NMR (C6D6, 100.6 MHz): d
151.7 (C–NMe2), 138.0 (m-CH), 125.3 (ipso-C–Sn), 113.4
(o-CH), 67.5 (OCH(CH3)2), 39.8 (N(CH3)2), 28.4
(OCH(CH3)2) ppm; 118Sn NMR (C6D6, 149.2 MHz): d
ꢀ66.6 ppm; Anal. Calc. for C27H37ON3Sn (538.312): C,
60.24; H, 6.93. Found: C, 60.12; H, 6.78%.
Ph2SnCl2 (2057 mg, 5.98 mmol) and LiNMe2 (670 mg,
13.14 mmol). Yield 1610 mg, 69%. M.p. 83–84 ꢁC (dec.).
The analytical data obtained were in agreement with those
previously reported [4].
2.3.6. (p-MeC6H4)2Sn(OiPr)2
(p-MeC6H4)2SnCl2 (974 mg, 2.62 mmol) and LiNMe2
2.3.11. (p-Me2NC6H4)2Sn(NMe2)2
(p-Me2NC6H4)2SnCl2 (2094 mg, 4.87 mmol) and
LiNMe2 (550 mg, 10.78 mmol). Yield 1900 mg, 87%. M.p.
(280 mg, 5.49 mmol). Yield 330 mg, 30%. M.p. 77-78 ꢁC
3
(dec.); 1H NMR (C6D6, 400 MHz): d 7.64 (d, JH–H
=
3
8 Hz, m-CH aryl, 4 H), 7.02 (d, JH–H = 8 Hz, o-CH aryl,
4 H), 4.47 (sept, JH–H = 6 Hz, OCH(CH3)2, 2 H), 2.04
(s, CH3, 6 H), 1.35 (d, JH–H = 6 Hz, OCH(CH3)2, 12 H)
75–76 ꢁC (dec.); 1H NMR (C6D6, 400 MHz): d 7.69 (d,
3
3
3JH–H = 8.4 Hz, m-CH aryl, 4 H), 6.66 (d, JH–H
=
3
8.4 Hz, o-CH aryl, 4 H), 3.11 (s, Sn–N(CH3)2, 12 H), 2.49
(s, p-N(CH3)2, 12 H) ppm; 13C NMR (C6D6,
100.6 MHz): d 151.7 (C–N(CH3)2), 138.0 (m-CH), 123.1
(ipso-C–Sn), 113.4 (o-CH), 44.1, (Sn–N(CH3)2), 39.7
(p-N(CH3)2) ppm; 118Sn NMR (C6D6, 149.2 MHz): d
ꢀ60.8 ppm; Anal. Calc. for C20H32N4Sn (447.205): C,
53.71; H, 7.21. Found: C, 53.44; H, 7.03%.
ppm; 13C NMR (C6D6, 100.6 MHz): d 140.6 (C–CH3),
136.5 (m-CH), 134.7 (ipso-C–Sn), 130.1 (o-CH), 67.7
(OCH(CH3)2), 28.0 (C–CH3), 21.4 (OCH(CH3)2) ppm;
118Sn NMR (C6D6, 149.2 MHz): d ꢀ 147.1 ppm; Anal.
Calc. for C20H28O2Sn (419.145): C, 57.31; H, 6.73. Found:
C, 57.19; H, 6.65%.
2.3.7. (p-MeC6H4)2Sn(NMe2)2
2.4. General procedure for the synthesis of
(p-XC6H4)3SnOiPr (X = CF3, F, Me)
3
1H NMR (C6D6, 250 MHz): d 7.60 (d, JH–H = 7.9 Hz,
3
m-CH aryl, 4 H), 7.07 (d, JH–H = 7.9 Hz, o-CH aryl,
4 H), 2.99 (s, N(CH3)2, 12 H), 2.08 (s, CH3, 6 H) ppm;
13C NMR (C6D6, 62.9 MHz): d 139.7 (C–CH3), 137.1 (m-
CH), 134.3 (ipso-C–Sn), 129.9 (o-CH), 43.9 (N(CH3)2),
21.4 (C–CH3) ppm.
Typically, a suspension of (p-XC6H4)3SnCl (1 equiv)
and LiOiPr (1.1 equiv) in benzene was vigorously stirred
for two days at room temperature and for ca 4 h at
60 ꢁC. After centrifugation and filtration of the mixture
all volatiles were removed under vacuum and the residues
were either recrystallized from hexanes at ꢀ40 ꢁC or dis-
tilled under vacuum (Kugelrohr apparatus) to yield analyt-
ically pure samples of the title compounds.
2.3.8. (p-MeOC6H4)2Sn(OiPr)2
(p-MeOC6H4)2SnCl2 (1031 mg, 2.56 mmol) and LiNMe2
(274 mg, 5.37 mmol). Yield 750 mg, 65%. 1H NMR (C6D6,
3
250 MHz): d 7.66 (d, JH–H = 8.8 Hz, m-CH aryl, 4 H),
3
6.83 (d, JH–H = 8.8 Hz, o-CH aryl, 4 H), 4.52 (sept,
2.4.1. (p-MeC6H4)3SnOiPr
3JH–H = 6 Hz, OCH(CH3)2, 2 H), 3.21 (s, CH3O, 6 H),
(p-MeC6H4)3SnCl (1735 mg, 4.06 mmol) and LiOiPr
(280 mg, 4.24 mmol). Yield 1340 mg, 73%. Bp. 135 ꢁC
3
1.40 (d, JH–H = 6 Hz, OCH(CH3)2, 12 H) ppm; 13C
NMR (C6D6, 100.6 MHz): d 162.1 (C–OMe), 138.0 (m-
CH), 128.1 (ipso-C–Sn), 115.2 (o-CH), 67.7 (OCH(CH3)2),
54.4 (CH3O), 28.3 (OCH(CH3)2) ppm; 118Sn NMR (C6D6,
149.2 MHz): d ꢀ133.7 ppm; Anal. Calc. for C20H28O4Sn
(451.144): C, 53.25; H, 6.26. Found: C, 52.98; H, 6.14%.
(4 · 10ꢀ2 mbar); 1H NMR (C6D6, 400 MHz): d 7.7 (d,
3
3JH–H = 7.6 Hz, m-CH aryl, 6 H), 7.06 (d, JH–H
=
3
7.6 Hz, o-CH aryl, 6 H), 4.42 (sept, JH–H = 6 Hz,
3
OCH(CH3)2, 1 H), 2.07 (s, CH3, 9 H), 1.36 (d, JH–H
=
6 Hz, OCH(CH3)2,
6
H) ppm; 13C NMR (C6D6,
62.9 MHz): d 139.8 (C–CH3), 137.0 (m-CH), 135.7 (ipso-
C–Sn), 129.9 (o-CH), 67.9 (OCH(CH3)2), 28.2 (C–CH3),
21.4 (OCH(CH3)2) ppm; 118Sn NMR (C6D6, 149.2 MHz):
d ꢀ85.9 ppm; Anal. Calc. for C24H28OSn (451.189): C,
63.89; H, 6.26. Found: C, 63.67; H, 6.05%.
2.3.9. (p-MeOC6H4)2Sn(NMe2)2
3
1H NMR (C6D6, 400 MHz): d 7.58 (d, JH–H = 8.4 Hz,
3
m-CH aryl, 4 H), 6.87 (d, JH–H = 8.4 Hz, o-CH aryl, 4
H), 3.29 (s, OCH3, 6 H); 3.00 (s, N(CH3)2, 12 H) ppm;