5586 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Synthesis of Thiocyanato(1,4,7,10,13,16-hexaoxacyclononadec-
18-methyl)diphenylstannane (6). To a solution of 3(1.02 g, 1.476
mmol) in CH3CN (50 mL) was added excess AgSCN (0.73 g, 4.427
mmol). The reaction mixture was stirred at room temperature and
in the dark for 10 days, followed by filtration of the AgI formed
and the nonreacted AgSCN. Removing the solvent in vacuo gave
0.55 g (60%) of 6 as slightly yellow oil.
1J(13C-119Sn) ) 294 Hz, Sn-CH2-Sn), 20.6 (1J(13C-117Sn) ) 471
Hz, 1J(13C-119Sn) ) 494 Hz, SnCH2), 38.1 (2J(13C-117/119Sn) )
20 Hz, C18), 70.0, 70.7, 70.9, 71.0, 71.2, 71.3, 71.4 (C2-C15),
74.5/74.8 (C17/C19), 128.8 (3J(13C-117/119Sn) ) 60 Hz, SnIPh,
Cm), 128.9 (3J(13C-117/119Sn) ) 52 Hz, SnPh3, Cm), 129.4
(4J(13C-117/119Sn) ) 12 Hz, SnPh3, Cp), 129.6 (4J(13C-117/119Sn)
) 12 Hz, SnIPh2, Cp), 135.4 (2J(13C-117/119Sn) ) 48 Hz, SnIPh,
Co), 137.7 (2J(13C- 117/119Sn) ) 39 Hz, SnPh3, Co), 139.7
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.59 (d, J(1H-1H) ) 4.0
(3J(13C-117/119Sn)
) ) 497 Hz,
14 Hz, 1J(13C-117Sn)
2
2
Hz, J(1H-117Sn) ) 68.0 Hz, J(1H-119Sn) ) 84.0 Hz, 2H, Sn-
CH2), 2.57 (m, 1H, CH), 3.44-3.76 (complex pattern, 24H, CH2-
O-CH2), 7.43-7.76 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 15.4 (C20), 37.4 (C18), 70.8, 70.9, 71.0, 71.2 (C2-C15),
75.1 (C17/C19), 128.3 (3J(13C-117/119Sn) ) 65 Hz, Cm), 130.3
(Cp), 136.3 (2J(13C-117/119Sn) ) 45 Hz, Co), 139.1 (Ci). 119Sn{1H}
NMR (CDCl3, 111.93 MHz) δ: -154 (t, 1J(119Sn-14N) ) 256 Hz).
Anal. Calcd for C27H37 NO6SSn (596.73): C 52.1; H 6.0; N 2.3.
Found: C 51.4; H 5.7; N 2.6.
1J(13C-119Sn) ) 521 Hz, SnPh3, Ci), 143.4 (3J(13C-117/119Sn) )
22 Hz, 1J(13C-117Sn) ) 547 Hz, 1J(13C-119Sn) ) 572 Hz, SnIPh2,
Ci). 119Sn{1H} NMR (CDCl3, 111.92 MHz) δ: -62 (2J (119Sn-117/
119Sn) ) 293/310 Hz, SnPh3), -85 (2J(119Sn-117/119Sn) ) 294/
312 Hz, SnIPh). Anal. Calcd (%) for C39H49IO6Sn2 (977.98): C
47.9, H 5.0. Found: C 48.1, H 4.9.
Synthesis of the Aqua Complex of 18-({Iodophenyl[(iododi-
phenylphenylstannyl)methyl]stannyl}methyl)-1,4,7,10,13,16-hexaox-
anonadecane (9 · H2O). Iodine (0.55 g, 2.154 mmol) was added
in small portions and under ice cooling to a stirred solution of
7 (1.0 g, 1.077 mmol) in CH2Cl2 (50 mL). The reaction mixture
was stirred while warming at room temperature overnight. The
solvent and the iodobenzene were removed in vacuo (10-3 mm
Hg) to afford a yellow oil. The oil was dissolved in ether (10
mL), and the solution was cooled at -20 °C for several days to
give 0.7 g (63%) of 9 as a yellow solid. Single crystals of 9 · H2O
(mp 68-70 °C) suitable for X-ray diffraction analysis were
obtained by slow evaporation of an ethanol solution of 9 at room
temperature.
Synthesis of 18-({Diphenyl[(triphenylstannyl)methyl]stannyl}me-
thyl)-1,4,7,10,13,16-hexaoxanonadecane (7). A solution of (bro-
momagnesiummethyl)triphenylstannane, prepared from (bro-
momethyl)triphenylstannane (2.27 g, 5.113 mmol) and magnesium
(0.13 g, 5.349 mmol) in THF (60 mL), wad added dropwise to
a stirred solution of iodo({1,4,7,10,13,16-hexaoxanonadec-18-
yl}methyl)diphenylstannane (3.0 g, 4.340 mmol) in THF (50
mL) for a period of 2 h. After the addition had been completed,
the reaction mixture was heated at reflux overnight and then
cooled to room temperature. Cold water (60 mL) was added,
and the mixture was extracted three times with 50 mL of ether.
The combined organic phases were dried with MgSO4 and the
solvents evaporated in vacuo to give the crude product. It was
purified by column chromatography (Al2O3, CH2Cl2, ethyl
acetate) to yield 1.11 g (27.5%) of 7 as a colorless oil.
1H NMR (CDCl3, 400.13 MHz) δ: 1.12/1.49 (ABX-type
resonance, 2J(1H-1H) ) 11.5 Hz, 3J(1H-1H) ) 7.1 Hz, 2H,
Sn-CH2), 1.73/1.93 (AB-type resonance, 2J(1H-1H) ) 11.3 Hz,
2J(1H-117Sn) ) 56.7 Hz, 2J(1H-119Sn) ) 78.0 Hz, 2H, Sn-
CH2-Sn), 2.24 (1H, CH), 3.21-3.64 (complex pattern, 24H, CH2-
O-CH2), 7.29-7.81 (15H, Ph). 13C NMR (CDCl3, 100.63 MHz)
δ: 4.0 (1J(13C-117Sn) ) 288/301 Hz, 1J(13C-119Sn) ) 324/
1H NMR (CDCl3, 400.13 MHz) δ: 0.81 (s, 2J(1H-117/119Sn) )
61.7 Hz, 2H, Sn-CH2-Sn), 1.01 (d, 3J(1H-117/119Sn) ) 7.5 Hz,
2
2J(1H-117Sn) ) 48 Hz, J(1H-119Sn) ) 64.0 Hz, 2H, Sn-CH2),
339 Hz, Sn-CH2-Sn), 20.9 (1J(13C-117Sn)
) 483 Hz,
2.13 (m, 1H, CH), 3.21-3.68 (complex pattern, 24H, CH2-O-CH2),
7.22-7.47 (25H, Ph). 13C NMR (CDCl3, 100.63 MHz) δ: -15.2
(1J(13C-117Sn) ) 262/273 Hz, 1J(13C-119Sn) ) 287/300 Hz, Sn-
1J(13C-119Sn) ) 505 Hz, SnCH2), 38.2 (2J(13C-117/119Sn) )
25 Hz, C18), 70.8, 71.0, 71.2, 71.3 (C2-C15), 74.5 (C17/C19),
129.0 (3J(13C-117/119Sn) ) 62 Hz, SnIPh, Cm), 129.2 (3J(13C-117/
119Sn) ) 63 Hz, SnIPh2, Cm), 129.8 (4J(13C-117/119Sn) ) 13
Hz, SnIPh, Cp), 130.4 (4J(13C-117/119Sn) ) 14 Hz, SnIPh2, Cp),
135.5 (2J(13C-117/119Sn) ) 48 Hz, SnIPh, Co), 137.0 (SnIPh2,
Co), 138.4 (SnIPh, Ci), 142.1 (3J(13C-117/119Sn) ) 28 Hz, SnIPh,
Ci). 119Sn{1H} NMR (CDCl3, 111.92 MHz) δ: -55 (2J (119Sn-117/
119Sn) ) 256 Hz, SnIPh2), -79 (2J(119Sn-117/119Sn) ) 261 Hz,
SnIPh). 119Sn MAS NMR (149.20 MHz) δ: -67, -171. Anal.
Calcd (%) for C33H44I2O6Sn2 · H2O (1045.94): C 37.9, H 4.4.
Found: C 37.8, H 4.3.
1
CH2-Sn), 12.5 (1J(13C-117Sn) ) 388 Hz, J(13C-119Sn) ) 406
Hz, SnCH2), 37.6 (2J(13C-117/119Sn) ) 19 Hz, C18), 70.8, 71.1,
71.2, 71.3 (C2-C15), 75.1 (C17/C19), 74.6 (3J(13C- 117/119Sn)
) 50 Hz, C17/C19), 128.5 (3J(13C-117/119Sn) ) 48 Hz, SnPh2,
Cm), 128.7 (SnPh2, Cp), 128.8 (3J(13C-117/119Sn) ) 48.3 Hz, SnPh3,
Cm), 129.1 (4J(13C-117/119Sn) ) 11 Hz, SnPh3, Cp), 136.9
(2J(13C-117/119Sn) ) 37 Hz, SnPh2, Co), 137.3 (2J(13C-117/119Sn)
) 38 Hz, SnPh3, Co), 140.2 (3J(13C-117/119Sn) ) 9 Hz,
1
1J(13C-117Sn) ) 483 Hz, J(13C-119Sn) ) 505 Hz, SnPh3, Ci),
142.2 (3J(13C-117/119Sn) ) 12 Hz, 1J(13C-117Sn) ) 457 Hz,
1J(13C-119Sn) ) 479 Hz, SnPh2, Ci). 119Sn{1H} NMR (CDCl3,
111.92 MHz) δ: -55 (2J(119Sn-117/119Sn) ) 231 Hz, SnPh2), -76
(2J(119Sn-117/119Sn) ) 227 Hz, SnPh3). Anal. Calcd (%) for
C45H54O6Sn2 (928.34): C 58.2, H 5.9. Found: C 58.2, H 6.0.
Synthesis of 5 · KF. Potassium fluoride (7.6 mg, 0.130 mmol)
was added to a solution of 5 (75.86 mg, 0.130 mmol) in CH2Cl2
(7 mL), and the mixture was stirred at room temperature for 2
days. The reaction mixture was filtered, and the filtrate was dried
over molecular sieves. n-Hexane (5 mL) was added, and slow
evaporation of the solvent gave 42.5 mg (51%) of 5 · KF as a
colorless crystalline solid, mp 230 °C. 1H NMR (CDCl3, 400.13
MHz, 293 K) δ: 1.26 (d, 3J(1H-1H) ) 8.0 Hz, 2J(1H-117/119Sn)
) 82.8 Hz, 2H, Sn-CH2), 2.55 (m, 1H, CH), 3.36-3.64 (complex
pattern, 24H, CH2-O-CH2), 7.28-8.16 (10H, Ph). 13C{1H} NMR
(CDCl3,100.63 MHz, 293 K) δ: 19.4 (C20), 36.0 (C18), 69.7,
69.8, 69.9, 70.2 (C2-C15), 76.4 (C17/C19), 127.6 (3J(13C-117/
119Sn) ) 67 Hz, Cm), 128.1 (Cp), 136.6 (2J(13C-117/119Sn) )
49 Hz, Co), 145.9 (broad, Ci). 19F{1H} NMR (CDCl3, 282.4
MHz, 293 K) δ: -157.7 (1J(19F-117Sn) )1838 Hz,
1J(19F-119Sn) ) 1912 Hz). 119Sn{1H} NMR (CDCl3, 111.92
MHz, 293 K) δ: - 277 (t, 1J(119Sn-19F) ) 1919 Hz). Anal.
Calcd (%) for C26H37F2KO6Sn (641.38): C 48.7, H 5.8. Found:
C 48.3, H 6.2.
Synthesis of 18-({Iodophenyl[(triphenylphenylstannyl)methyl]-
stannyl}methyl)-1,4,7,10,13,16-hexaoxanonadecane (8). Iodine (107.1
mg, 0.422 mmol) was added in small portions and under ice
cooling to a stirred solution of 7 (392.0 mg, 0.422 mmol) in
CH2Cl2 (20 mL). Stirring was continued while warming to room
temperature overnight. The solvent and the iodobenzene were
removed in vacuo (10-3 mmHg) to afford a slightly yellow oil.
The oil was dissolved in ethanol (8 mL), and the solution was
cooled at -15 °C for some days to give 260.0 mg (60.2%) of 8
as a colorless crystalline solid, mp 88-90 °C.
1H NMR (CDCl3, 400.13 MHz) δ: 0.91 (dd, 2J(1H-1H) ) 13.1
3
Hz, J(1H-1H) ) 6.5 Hz, 1H, Sn-CHH′), 1.25-1.46 (m, 3H, Sn-
CHH′-Sn and Sn-CH2-Sn), 2.10 (m, 1H, CH), 3.14-3.76 (complex
pattern, 24H, CH2--O-CH2), 7.34-7.76 (20H, Ph). 13C NMR
(CDCl3, 100.63 MHz) δ: -5.7 (1J(13C-117Sn) ) 282 Hz,