3278 Organometallics, Vol. 19, No. 17, 2000
Beckmann et al.
a
second reference (-97.35 ppm against Me4Sn) and to
1,1,3,3,5,5,7,7,9,9-Deca p h en yl-4,6,8,10-tetr a oxa -1,3-d is-
optimize Hartmann-Hahn matching conditions. Mass spectra
were measured on a Finnigan MAT 8230 spectrometer. Elec-
trospray mass spectra were obtained with
ta n n a -5,7,9-tr isila cyclod eca n e (3). Yield: 2.32 g, 1.98 mmol,
1
79%; mp 115 °C. H NMR (CDCl3) δ: 7.7-7.1 (50 H, m; Ph),
0.95 (2H, s, 2J (119Sn-1H) ) 59 Hz; SnCH2Sn). 13C{1H} NMR
(CDCl3) δ: 139.9 (SnPhCi), 137.6 ((SiO)2SiPhCi), 135.9 (SnO-
SiPhCi), 135.8 (SnPhCo), 134.7 ((SiO)2SiPhCo), 134.5 (SnO-
SiPhCo), 129.6 (SnPhCp), 129.4 ((SiO)2SiPhCp), 129.1 (SnO-
SiPhCp), 128.5 (SnPhCm), 127.3 ((SiO)2SiPhCm), 127.2 (SnOSi-
PhCm), -5.91 (SnCH2Sn). 29Si{1H} NMR (CDCl3) δ: -42.2
(2J (29Si-O-117/119Sn) ) 33 Hz; SnOSi), -46.8 ((SiO)2Si). 119Sn-
{1H} NMR (CDCl3) δ: -26.1 (2J (119Sn-C-117Sn) ) 474 Hz,
a Micromass
Platform II single quadrupole mass spectrometer using an
acetonitrile mobile phase. Acetonitrile/dichloromethane solu-
tions (1:1; c ) 1 × 10-3 mol L-1) of the compounds were injected
directly into the spectrometer via a Rheodyne injector equipped
with a 50 µL loop. A Harvard 22 syringe pump delivered the
solutions to the vaporization nozzle of the electrospray ion
source at a flow rate of 10 µL min-1. Nitrogen was used both
as a drying gas and for nebulization with flow rates of
approximately 200 and 20 mL min-1 respectively. Pressure
in the mass analyzer region was usually about 4 × 10-5 mbar.
Typically 10 signal-averaged spectra were collected. Ions
showed the expected isotopic pattern. Elemental analyses were
performed on an instrument from Carlo Erba Strumentazione
(model 1106). The density of single crystals was determined
using a Micromeritics Accu Pyc 1330.
2J (119Sn-O-29Si) ) 33 Hz). MS m/z (%): 896 (8) [M+ - C12H10
-
Sn], 696 (4) [M+ - C25H22SiSn], 636 (13) [M+ - C30H20O3Si3],
594 (32) [M+ - C25H22OSn2]. Anal. Calcd for C61H52O4Si3Sn2
(1170.81): C, 62.58; H, 4.48. Found: C, 62.6; H, 4.5.
1,1,3,3,5,5,7,7,9,9,11,11-Dod eca p h en yl-4,6,8,10,12-p en -
ta oxa -1,3-d ista n n a -5,7,9,11-tetr a sila cyclod od eca n e (4).
1
Yield: 2.51 g, 1.85 mmol, 74%; mp 182 °C. H NMR (CDCl3)
2
δ: 7.7-7.1 (60H, m; Ph). 0.94 (2H, s; J (119Sn-1H) ) 63 Hz;
SnCH2Sn). 13C{1H} NMR (CDCl3) δ: 141.2 (SiPhCi), 139.5
(SiPhCi), 137.1 (SiPhCi), 137.8 (SnPhCo), 136.7 (SiPhCo), 136.6
(SiPhCo), 131.7 (SiPhCp), 131.6 (SiPhCp), 131.2 (SnPhCp), 130.5
5 (SnPhCm), 129.5 (SiPhCm), 129.4 (SiPhCm), -2.04 (SnCH2-
Sn). 29Si{1H} NMR (CDCl3) δ: -42.1 (2J (29Sn-O-117/119Sn) )
33 Hz; SnOSi), -47.5 ((SiO)2Si). 119Sn{1H} NMR (CDCl3) δ:
-26.9 (2J (119Sn-C-117Sn) ) 551 Hz, 2J (119Sn-O-29Si) ) 33
Ca ta lytic Con d en sa tion of Dip h en ylsila n d iol. A mix-
ture of [Ph2(OH)Sn]2CH2 (1.19 g, 2.00 mmol) and Ph2Si(OH)2
(4.32 g, 20.0 mmol) in acetone (50 mL) was heated at 60 °C.
After 20 h a colorless precipitate of cyclo-(Ph2SiO)4 was filtered
(2.53 g, 3.19 mmol, 64%). 29Si{1H} NMR (CDCl3) δ: -42.7.
Anal. Calcd for C48H40O4Si4 (793.19): C, 72.69; H, 5.08.
Found: 72.6; H, 5.1.
In Situ Syn th esis of 1,1,3,3,5,5-Hexa p h en yl-4,6-d ioxa -
1,3-d ista n n a -5-sila cycloh exa n e (1). A mixture of [Ph2(OH)-
Sn]2CH2 (29.7 mg, 0.05 mmol) and Ph2Si(OH)2 (10.8 mg, 0.05
mmol) in CDCl3 (300 µL) was heated at 60 °C for 30 min,
resulting in a clear solution. 119Sn and 29Si NMR spectroscopy
showed the exclusive formation of 1. 29Si{1H} NMR (CDCl3)
δ: -34.0 (2J (29Si-O-117/119Sn) ) 25 Hz. 119Sn{1H} NMR (CDCl3)
δ: -34.7 (2J (119Sn-C-117Sn) ) 512 Hz, 2J (119Sn-O-29Si) ) 25
Hz). Then the mixture was heated again at 60 °C for 2 days.
During this period the solution was investigated by 119Sn and
29Si NMR spectroscopy, which revealed increasing amounts
of 2. After a short time a colorless precipitate was observed,
which was not filtered.
The above reaction was repeated on a preparative scale
using [Ph2(OH)Sn]2CH2 (1.48 g, 2.50 mmol) and Ph2Si(OH)2
(0.54 g, 2.50 mmol) in toluene (25 mL): The precipitate was
filtered. It consisted exclusively of [Ph2(OH)Sn]2CH2, which
was identified by elemental analysis and by comparison of its
IR spectrum with that of an authentic sample. The filtrate
was evaporated in vacuo ,and the solid residue was crystallized
from hexane/dichloromethane, affording 2 (0.86 g, 0.88 mmol,
35%, mp 110 °C).
Syn th esis of th e cyclo-Meta lla sta n n oxa n es 2-6. A
mixture of [Ph2(OH)Sn]2CH2 (1.49 g, 2.5 mmol) and 2.5 mmol
of the corresponding silanol (1.04 g [Ph2(OH)Si]2O for 2, 1.53
g [Ph2(OH)SiO]2SiPh2 for 3, 2.03 g [Ph2(OH)SiOSiPh2]2O for
4, and 0.44 g t-Bu2Si(OH)2 for 5) or germane diol (0.55 g t-Bu2-
Ge(OH)2 for 6), respectively, in toluene (25 mL) was heated at
60 °C in an open flask, resulting in a clear solution. The solvent
was removed in vacuo, and the solid residue was crystallized
from hexane/dichloromethane (1:1) to give the cyclo-metal-
lastannoxanes 2-6.
Hz). MS m/z (%): 890 (16) [M+ - C18H15OSi], 813 (7) [M+
-
-
C
C
24H20OSi], 637 (48) [M+ - C42H35O5Si4), 558 (28) [M+
48H40O5Si4]. Anal. Calcd for C73H62O5Si4Sn2 (1357.10): C,
63.72; H, 4.60. Found: C, 64.2; H, 4.6.
1,1,3,3-Tetr a p h en yl-5,5-d i-ter t-bu tyl-4,6-d ioxa -1,3-d is-
ta n n a -5-sila cycloh exa n e (5). Yield: 1.75 g, 2.38 mmol, 95%;
1
mp 148 °C. H NMR (CDCl3) δ: 7.6-7.20 (20H, m; Ph), 0.96
(2H, s, 2J (1H-119Sn) ) 53 Hz; SnCH2Sn), 0.85 (18H, s; SiCMe3).
13C{1H} NMR (CDCl3) δ: 140.1 (SnPhCi), 135.4 (SnPhCo),
129.4 (SnPhCp), 128.2 (SnPhCm), 27.8 (SiCMe3), 21.0 (SiCMe3),
-8.1 (SnCH2Sn). 29Si{1H} NMR (CDCl3) δ: -13.5 (2J (29Si-O-
117/119Sn) ) 39 Hz). 119Sn{1H} NMR (CDCl3) δ: -42.8 (2J (119Sn-
C-117Sn) ) 551 Hz, 2J (119Sn-O-29Si) ) 39 Hz). 119Sn{1H} MAS
NMR δ: -34.2, -35.2. MS m/z (%): 676 (100) [M+ - C4H9],
634 (30) [M+ - C5H12], 556 (27) [M+ - C10H17]. Anal. Calcd for
C
33H40O2SiSn2 (734.24): C, 53.98; H, 5.49. Found: C, 54.0; H,
5.9.
1,1,3,3-Tetr a p h en yl-5,5-d i-ter t-bu tyl-4,6-d ioxa -1,3-d is-
ta n n a -5-ger m a cycloh exa n e (6). Yield: 1.60 g; 2.05 mmol,
82%; mp 117 °C. 1H NMR (CDCl3) δ: 7.7-7.2 (20H, m; Ph),
1.05 (2H, s, SnCH2Sn), 1.13 (18H, s, SiCMe3). 13C{1H} NMR
(CDCl3) δ: 141.6 (SnPhCi), 135.8 (SnPhCo), 129.5 (SnPhCp),
128.7 (SnPhCm), 30.1 (GeCMe3), 28.1 (GeCMe3), -7.0 (SnCH2-
Sn). 119Sn{1H} NMR (CDCl3) δ: -38.3 (2J (119Sn-C-117Sn) )
508 Hz). 119Sn{1H} MAS NMR δ: -30.2, -33.7, -37.4, -40.8.
MS m/z (%): 721 (92) [M+ - C4H9], 664 (10) [M+ - C8H18],
577 (45) [M+ - C8H18Ge], 499 (10) [M+ - C14H23Ge], 421 (8)
[M+ - C20H28Ge]. Anal. Calcd for C33H40O2GeSn2 (778.78): C,
50.90; H, 5.18. Found: C, 50.9; H, 5.2.
In Situ Rea ction of cyclo-O(P h 2SiOSn P h 2)2CH2 (2) a n d
cyclo-P h 2Si(OP h 2SiOSn P h 2)2CH 2 (3) w it h P h 2Si(OH )2.
Equimolar quantities of Ph2Si(OH)2 (19 mg, 0.088 mmol) and
cyclo-O(Ph2SiOSnPh2)2CH2 (2) (85.6 mg, 0.088 mmol) (case A)
or cyclo-Ph2Si(OPh2SiOSnPh2)2CH2 (3) (103 mg, 0.088 mmol)
(case B) were dissolved in CDCl3 to give clear solutions. From
these solutions, 29Si and 119Sn NMR spectra were recorded,
the results of which are given below.
1,1,3,3,5,5,7,7-Octa p h en yl-4,6,8-tr ioxa -1,3-d ista n n a -5,7-
d isila cycloocta n e (2). Yield: 1.96 g, 2.02 mmol, 81%; mp 110
°C. 1H NMR (CDCl3) δ: 7.7-7.1 (40H, m; Ph), 0.87 (2H, s,
2J (1H-119Sn) ) 55 Hz; SnCH2Sn). 13C{1H} NMR (CDCl3) δ:
139.9 (SnCi), 138.2 (SiCi), 135.8 (SnCo), 134.4 (SiCo), 129.7,
(SnCp), 129.0 (SiCp), 128.6, (SnCm), 127.3 (SiCm), -5.22 (SnCH2-
Sn). 29Si{1H} NMR (CDCl3) δ: -41.0 (2J (29Si-O-117/119Sn) )
36 Hz). 119Sn{1H} NMR (CDCl3) δ: -29.8 (2J (119Sn-C-117Sn)
Case A: 3 (δ 119Sn -26.1, 2J (119Sn-C-117Sn) 474 Hz,
integral 41; δ 29Si -42.2, 2J (29Si-O-117/119Sn) 33 Hz, δ 29Si
2
-46.8), 2 (δ 119Sn -29.8, J (119Sn-C-117Sn) 535 Hz, integral
2
) 535 Hz, J (119Sn-O-29Si) ) 36 Hz). 119Sn{1H} MAS NMR
δ: -18.8, -25.5, -30.7, -31.8. MS m/z (%): 816 (14) [M+
-
48; δ 29Si -41.0, 2J (29Si-O-117/119Sn) 36 Hz), 1 (δ 119Sn -34.7,
integral 4.5; δ 29Si -34.0, 2J (29Si-O-117/119Sn) 25 Hz), 4 (δ 119Sn
C
12H10], 697 (12) [M+ - C25H22SiSn], 637 (12) [M+ - C18H15O3-
2
Si3], 594 (26) [M+ - C25H22OSn2]. Anal. Calcd for C49H42O3-
Si2Sn2 (972.51): C, 60.52; H, 4.35. Found: C, 60.5; H, 4.4.
-26.9, integral 5.7; δ29Si -42.1 J (29Si-O-117/119Sn) 33 Hz, δ
29Si -47.5), Ph2Si(OSiPh2OH)2 (δ 29Si -36.1, -44.2), O(SiPh2-