1,1,3,3,5,5,7,7-Octaphenyl-1,3,5,7-tetrasiloxane-1,7-diol and Its Organotin Derivatives. Model Compounds for Diphenylsiloxane Polymer

Article abstract of DOI:10.1021/om990107z

The hydrolysis of the spirotitanasiloxane Ti[(OSiPh₂)₄O]₂ provides 1,1,3,3,5,5,7,7-octaphenyl-1,3,5,7-tetrasiloxane-1,7-diol, H(OSiPh₂)₄OH (1), in high yield. The reaction of 1 with tricyclohexyltin h

Full text of DOI:10.1021/om990107z

2326
Organometallics 1999, 18, 2326-2330
1,1,3,3,5,5,7,7-Octa p h en yl-1,3,5,7-tetr a siloxa n e-1,7-d iol a n d
Its Or ga n otin Der iva tives. Mod el Com p ou n d s for
Dip h en ylsiloxa n e P olym er †
J ens Beckmann,‡ Klaus J urkschat,*,‡ Dirk Mu¨ller,§ Stephanie Rabe,‡ and
Markus Schu¨rmann‡
Lehrstuhl fu¨r Anorganische Chemie II, Fachbereich Chemie der Universita¨t Dortmund,
D-44221 Dortmund, Germany, and Institut fu¨r Angewandte Chemie,
Rudower Chaussee 5, D-12484 Berlin, Germany
Received February 17, 1999
The hydrolysis of the spirotitanasiloxane Ti[(OSiPh2)4O]2 provides 1,1,3,3,5,5,7,7-octaphen-
yl-1,3,5,7-tetrasiloxane-1,7-diol, H(OSiPh2)4OH (1), in high yield. The reaction of 1 with
tricyclohexyltin hydroxide, cyclo-Hex3SnOH, and di-tert-butyltin oxide, cyclo-(t-Bu2SnO)3,
respectively, gives 1,1,3,3,5,5,7,7-octaphenyl-1,7-tricyclohexylstannyl-1,3,5,7-tetrasiloxane,
(cyclo-Hex3SnOSiPh2OSiPh2)2O (2), and 1,1-di-tert-(butyl-3,5,7,9-octaphenyl-2,4,6,8,10-pen-
taoxa-,3,5,7,9-tetrasila-1-stannacyclododecane, cyclo-t-Bu2Sn(OSiPh2OSiPh2)2O (3). The mo-
lecular structures of 1 and 2 were determined by X-ray diffraction. In both compounds the
central Si-O-Si angle amounts to 180°. Remarkably, no hydrogen bonding is observed for
1.
In tr od u ction
(methyl/trifluoropropyl)-, and poly(methyl/phenyl)silox-
ane.5 In contrast to these polysiloxanes which show a
high flexibility, the steric hindrance of the phenyl groups
in poly(diphenyl)siloxane causes a certain ridgidity
which is responsible for the high crystallinity of this
polymer. Above its melting point of 260 °C a transition
into a mesomorphic liquid crystalline phase takes place.6
The major advantage over other liquid crystals is that
PDPhS can be obtained with almost any chain length
by using anionic polymerization techniques.5b However,
the conformational analysis of PDPhS was the subject
of controversal discussions,7 and consequently, molec-
ular structures of any model compounds resembling
PDPhS are welcome.8
For some time we have been interested in the chem-
istry of stannasiloxanes, and recently we reported [Ot-
Bu2SnOSiPh2OSiPh2O]n, which is the first well-defined
polystannasiloxane in the solid state.9 However, in
solution this polymer reversibly turns into the corre-
sponding six-membered stannasiloxane ring cyclo-(t-Bu2-
The hydrolysis of organochlorosilanes gives either
organosiloxanes or organosil(ox)anols. Which of these
products is obtained depends on the reaction conditions
applied and/or on the steric bulk of the organic substit-
uents.1
The hydrolysis of diphenyldichlorosilane Ph2SiCl2
leads to oligomeric diphenylsiloxanes of the type cyclo-
(Ph2SiO)n (n ) 3, 4)2 or diphenylsil(ox)anols of the type
HO(Ph2SiO)nH (n ) 1-3).2,3 The hydrolysis of cyclo-(Ph2-
SiO)4 was reported to give HO(Ph2SiO)4H in rather low
yield.2c
Polymeric diphenylsiloxane, hereafter referred to as
PDPhS, is prepared either by ring-opening polymeriza-
tion (ROP) under nonequilibrium conditions of the six-
4
membered ring (Ph2SiO)3 or by condensation of oligo-
diphenylsiloxanols with diorganochlorosilanes.2j Because
of their excellent thermal and chemical stability, there
is a variety of applications for poly(dimethyl)-, poly-
† Dedicated to Professor Friedo Huber on the occasion of his 70th
birthday. This paper contains part of the intended Ph.D. Thesis of
Stephanie Rabe.
(4) (a) Buzin, M. I.; Gerasimov, M. V.; Obolonkova, E. S.; Papkov,
V. S. J . Polym. Sci. Part A, Polym. Chem. 1997, 35, 1973. (b) Harkness,
B. H.; Tachikawa, M.; Yue, H.; Mita, I. Chem. Mater. 1998, 10, 1700.
(5) (a) Lee, M. K.; Meier, D. J . Polymer 1993, 34, 4882. (b) Lee, M.
K.; Meier, D. J . Polymer 1993, 35, 3282. (c) Chou, C.; Yang, M. H. J .
Therm. Anal. 1993, 40, 657.
‡ Dortmund University.
§ Institut fu¨r Angewandte Chemie.
(1) Gmelin Handbook of Inorganic Chemistry, 8th ed.; Springer-
Verlag: Berlin, 1958; Part 15C.
(2) (a) Dilthey, W. Ber. 1905, 4132. (b) Kipping, F. S. J . Chem. Soc.
1912, 101, 2125. (c) Kipping, F. S.; Robinson, R. J . Chem. Soc. 1914,
105, 484. (d) Kipping, F. S. J . Chem. Soc. 1927, 2728. (e) Burkhard,
C. A. J . Am. Chem. Soc. 1945, 67, 2173. (f) Hyde, J . F.; Frevel, L. K.;
Nutting, H. S.; Petrie, P. S.; Purcel, M. A. J . Am. Chem. Soc. 1947, 69,
488. (g) Young, C. W.; Servais, P. C.; Currie, C. C.; Hunter, M. J . J .
Am. Chem. Soc. 1948, 70, 3758. (h) Braga, D.; Zanotti, G. Acta
Crystallogr. 1980, B36, 950. (i) Tomlins, P. E.; Lydon, J . E.; Akrogg,
D.; Sheldrick, B. Acta Crystallogr. 1985, C41, 292. (j) Harkness, B.
H.; Tachikawa, M. Chem. Mater. 1998, 10, 1706.
(3) (a) Fawcett, J . K.; Camerman, N.; Camerman, A. Can. J . Chem.
1977, 55, 3631. (b) Pa´rka´nyi, L.; Bocelli, G. Cryst. Struct. Commun.
1978, 7, 335. (c) Hossain, M. A., Hursthouse, M. B. J . Crystallogr.
Spectrosc. Res. 1988, 18, 227. (d) Behbehani, H.; Brisdon, B. J .; Mahon,
M. F.; Molloy, K. C. J . Organomet. Chem. 1993, 463, 41.
(6) (a) Harkness, B.; Tachikawa, M.; Mita, I. Macromolecules 1995,
28, 1323. (b) Harkness, B. R.; Tachikawa, M.; Mita, I. Macromolecules
1995, 28, 8136. (c) Li, L. J .; Yang, M. H. Polymer 1998, 39, 689.
(7) (a) Dubchak, I. L.; Babchinister, T. M.; Kazaryan, L. G.;
Tartakovskaya, L. M.; Vasilenko, N. G.; Zhdanov, A. A.; Korshak, V.
V. Polym. Sci. USSR (Engl. Transl.) 1989, 31, 70. (b) Grigoras, S.; Qian,
C.; Crowder, C.; Harkness, B.; Mita, I. Macromolecules 1995, 28, 7370.
(c) Papkov, V. S., Gerasimov, M. V.; Buzin, M. I.; Il’ina, M. N.;
Kazaryan, L. G. Polym. Sci. Ser. A 1996, 38, 1097.
(8) Brisdon, B. J .; Mahon, M. F.; Molloy, K. C.; Schofield, P. J . J .
Organomet. Chem. 1994, 465, 145.
(9) (a) Beckmann, J .; J urkschat, K.; Schollmeyer, D.; Schu¨rmann,
M. J . Organomet. Chem. 1997, 543, 229. (b) Beckmann, J .; Mahieu,
B.; Nigge, W.; Schollmeyer, D.; Schu¨rmann, M.; J urkschat, K. Orga-
nometallics 1998, 17, 5697.
10.1021/om990107z CCC: $18.00 © 1999 American Chemical Society
Publication on Web 05/20/1999

Model Compounds for Diphenylsiloxane Polymer
Organometallics, Vol. 18, No. 12, 1999 2327
Sch em e 1
SnOSiPh2)2O. In comparison to its parent system (Ph2-
SiO)n, the formal replacement of one Ph2SiO group by
a t-Bu2SnO group decreases the barrier between the six-
membered ring and its polymer and allows the study of
the interplay of ring strain on one hand and entropic
favor of various species in solution on the other hand.
Characteristic features of the polymer are the zigzag
chain conformation and the Si-O-Si angle of 180°.
The template-driven synthesis of the spirotitana-
siloxane Ti[(OSiPh2)4O]2 from Ph2Si(OH)2 and Ti(i-OPr)4
was first reported by Zeitler and Brown in 1957.10a Its
molecular structure was established more recently by
Hursthouse and Hossain.10b
Here we describe the hydrolysis of Ti[(OSiPh2)4O]2 to
give 1,1,3,3,5,5,7,7-octaphenyltetrasiloxy-1,7-diol, H(OSi-
Ph2)4OH (1). Former investigations concerning the
hydrolysis of spirotitanasiloxanes concentrated mainly
on kinetic aspects.11
Organosil(ox)anols are useful building blocks for the
synthesis of metallasiloxanes, the chemistry of which
has been reviewed recently.12 The reaction of 1 with
tricyclohexyltin hydroxide and di-tert-butyltin oxide,
respectively, gives the open-chain and cyclic stanna-
siloxanes 2 and 3. Stannasiloxane 2 and the diol 1 can
be regarded as model compounds for polydiphenylsilox-
anes.
compared to Ph2Si(OH)2 (δ -32.4 ppm),13 H(OSiPh2)2-
OH (δ -36.0 ppm),3d and H(OSiPh2)3OH (δ -36.5, -44.0
ppm; 2:1).3d The 29Si MAS NMR chemical shifts of -39.7
and -47.8 ppm are very similar to those in solution.
Thermally equilibrated PDPhS shows 29Si MAS NMR
chemical shifts of -43.6, -46.0, -46.6, and -47.7 ppm,
whereas pure (Ph2SiO)3 and (Ph2SiO)4 show signals at
-33.8 and -42.7 ppm, respectivly.4b The replacement
of the two hydroxy protons in the siloxanol 1 by
tricyclohexyltin moieties in compound 2 and the di-tert-
butyltin fragment in the 10-membered stannasiloxane
ring 3 results in low-frequency shifts of the 29Si NMR
resonances of the adjacent silicon atoms, whereas the
chemical shifts of the two other silicon atoms are not
affected (2, δ 29Si -45.8 (2J (29Si-O-117/119Sn) 70 Hz, Si-
O-Sn), -47.7 (Si-O-Si); 3, δ 29Si -44.9 (2J (29Si-O-
117/119Sn) 69 Hz, Si-O-Sn), -47.4 (Si-O-Si)). The
resonances observed for 10-membered stannasiloxane
ring 3 are close to the values measured for the related
eight-membered stannasiloxane ring cyclo-t-Bu2Sn-
(OSiPh2O)2SiPh2 (δ 29Si -43.2, -45.8).9b The 29Si MAS
NMR spectrum of the stannasiloxane 2 shows two
signals at -46.2 and -46.8 ppm, being comparable with
the chemical shifts found in solution. The 29Si MAS
NMR spectrum of the 10-membered cyclostannasiloxane
3 shows four signals at -44.7, -47.4, -49.1, and -50.2
ppm, respectively, which hints at four crystallographi-
cally inequivalent silicon atoms in the solid state.
The molecular structures of compounds 1 and 2 are
shown in Figures 1 and 2, respectively. Selected bond
lengths and bond angles are given in Table 1.
Resu lts a n d Discu ssion
1,1,3,3,5,5,7,7-Octaphenyltetrasiloxy-1,7-diol, H(OSi-
Ph2)4OH (1), was obtained in high yield by the hydroly-
sis of spiro-Ti[(OSiPh2)4O]2 in THF/H2O (eq 1).
The reaction of the organosil(ox)anol 1 with tricyclo-
hexyltin hydroxide, cyclo-Hex3SnOH, and di-tert-butyl-
tin oxide, cyclo-(t-Bu2SnO)3, respectively, afforded
1,1,3,3,5,5,7,7-octaphenyl-1,7-tricyclohexylstannyl-1,3,5,7-
tetrasiloxane, (cyclo-Hex3SnOSiPh2OSiPh2)2O (2), and
1,1-di-tert-butyl-3,5,7,9-octaphenyl-2,4,6,8,10-pentaoxa-
3,5,7,9-tetrasila-1-stannacyclododecane, cyclo-t-Bu2Sn-
(OSiPh2OSiPh2)2O (3), in good yields (Scheme 1).
The organosil(ox)anol 1 as well as the stannasiloxanes
2 and 3 are colorless, sharp melting solids and well
soluble in common organic solvents, such as CH2Cl2,
toluene, and thf. Compound 3 is even soluble in n-
hexane.
The most important features to be noticed are (i) the
absence of any Si-O‚‚‚H‚‚‚O hydrogen bridges in the
1,3,5,7-tetrasiloxane-1,7-diol derivative 1, which is in
sharp contrast to any other structurally characterized
organosilanol and organosil(ox)anol, respectively14a-c
and which illustrates the qualitative change in the
structures of Ph2(OH)Si(OSiPh2O)nSi(OH)Ph2 on going
from n ) 13d to n ) 2, and (ii) the Si(1)-O-Si(1a) angles
of 180° in both 1 and its tricyclohexyltin derivative 2.
The identity in solution of compounds 1-3 was
confirmed by NMR spectroscopy and molecular weight
determinations. The 29Si NMR (CDCl3) spectrum of 1
shows two equally intense signals at -36.9 and -45.3
ppm, respectively, which are in the expected region as
(10) (a) Zeitler, V. A.; Brown, C. A. J . Am. Chem. Soc. 1957, 79,
4618. (b) Hursthouse, M. B.; Hossain, M. A. Polyhedron 1984, 3, 95.
(11) (a) Hoebbel, D.; Reinert, T.; Schmidt, H. J . Sol-Gel Sci. Technol.
1996, 6, 139. (b) Hoebbel, D.; Nacken, M.; Schmidt, H.; Huch, V.; Veith,
M. J . Mater. Chem. 1998, 8, 171.
(12) Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W.
Chem. Rev. 1996, 96, 2205.
(13) Marsmann, H. C. NMR Principles and Progress 17, 29Si NMR
Spectroscopic Results; Diehl, P., Fluck, E., Kosfeld, R., Eds.; Springer-
Verlag: Berlin, 1981.
(14) (a) Lickiss, P. D. Adv. Inorg. Chem. 1995, 42, 147. (b) Unno,
M.; Takada, K.; Matsumoto, H. Chem. Lett. 1998, 489. (c) Minkwitz,
R.; Schneider, S. Z. Naturforsch. 1998, 53b, 426. (d) J arvie, A. W.; Holt,
A.; Thompson, J . J . Organomet. Chem. 1968, 11, 623.

2328 Organometallics, Vol. 18, No. 12, 1999
Beckmann et al.
F igu r e 3. Side view (SHELXTL-PLUS) of the unit cell of
1 (all phenyl groups were omitted for clarity).
F igu r e 1. General view (SHELXTL-PLUS) of a molecule
of 1 showing 30% probability displacement ellipsoids and
the atom-numbering scheme (symmetry transformation
used to generate equivalent atoms: a ) -x+1, -y+1, -z).
Ta ble 1. Cr ysta llogr a p h ic Da ta of 1 a n d 2
1
2
formula
fw, g/mol
cryst syst
cryst size, mm
space group
a, Å
C
48H42O5Si4
C84H106O5Si4Sn2
1545.43
triclinic
811.18
monoclinic
0.40 × 0.20 × 0.20 0.20 × 0.20 × 0.20
P21/n
P1h
10.150(1)
9.729(1)
21.643(1)
90
94.967(1)
90
2129.2(3)
2
1.265
10.247(1)
10.413(1)
19.791(1)
76.756(1)
79.305(1)
86.038(1)
2019.1(3)
1
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
F
F
calcd, Mg/m3
meas, Mg/m3
1.271
1.275(2)
0.726
1.256(1)
0.186
852
µ, mm-1
F igu r e 2. General view (SHELXTL-PLUS) of a molecule
of 2 showing 30% probability displacement ellipsoids and
the atom-numbering scheme (symmetry transformation
used to generate equivalent atoms: a ) -x, -y, -z).
F(000)
806
θ range, deg
4.18-25.67
-10 e h e 10
-11 e k e 11
-26 e l e 26
28415
4.09-25.88
-12 e h e 12
-10 e k e 11
-23 e l e 24
23692
index ranges
Both features make compounds 1 and 2 the first true
subunits9a showing the structural characteristics of
PDPhS and of [Ot-Bu2SnOSiPh2OSiPh2O]n. In analogy
to previously reported (Ph3SnO)Ph2SiOSiPh2(OSnPh3),8
compounds 1 and 2 adopt a staggered configuration
about the vector joining Si(1)-Si(1a), as is illustrated
by the corresponding dihedral angles across this vector,
i.e., C(1)-Si(1)-Si(1a)-C(1a) (1)/(2), C(11)-Si(1)-
Si(1a)-C(11a) (1)/(2), O(2)-Si(1)-Si(1a)-O(2a) (1)/(2)
of 180°.
no. of reflns collcd
completeness to θmax
92.6
91.4
7173/0.042
2720
no. of indep reflns/Rint 3743/0.024
no. of reflns obsd
with (I > 2σ(I))
no. of refined params
GoF (F2)
R1 (F) (I > 2σ(I))
wR2 (F2) (all data)
(∆/ σ)max
2640
343
476
0.804
0.0457
0.1045
<0.001
0.237/-0.272
1.015
0.0380
0.1026
<0.001
largest diff peak/hole, 0.380/-0.298
e/Å3
The molecular structure of the 1,3,5,7-tetrasiloxane-
1,7-diol derivative 1 shows the O(1)-bonded hydrogen
to point in the direction of the carbon atom C(21)
(H(1)‚‚‚C(21) 2.85(5) Å, H(1)-O(1)-Si(2)-C(21)
-23.4(7)°), which probably indicates weak hydrogen
interaction with the corresponding phenyl group and
explains the infrared spectrum of compound 1, as it was
reported in 1968.14d
Recently it was suggested that PDPhS realizes zigzag
chains in the solid state7 rather than a helical structure.
This view is supported by the structures of the 1,3,5,7-
tetrasiloxane-1,7-diol derivative 1 (Figure 3), of its
tricyclohexyltin derivative 2, and of the polystanna-
siloxane [Ot-Bu2SnOSiPh2OSiPh2O]n.9
Exp er im en ta l Section
Gen er a l Da ta . All solvents were dried according to stan-
dard procedures and freshly distilled prior to use. spiro-Ti-
[(OSiPh2)4O]2,10a cyclo-(t-Bu2SnO)3,15a and cyclo-Hex3SnOH15b
were synthesized according to literature procedures. Solution
1H, 13C, 29Si, and 119Sn NMR spectra were recorded on a Bruker
DRX 400 spectrometer and were referenced to SiMe4 (1H, 13C,
29Si) or SnMe4 (119Sn) in chloroform. 119Sn MAS NMR spectra
were obtained from a Bruker MSL 400 spectrometer using
cross-polarization and high-power proton decoupling. Chemical
shifts (δ) are given in ppm. Tetracyclohexyltin, cyclo-Hex4Sn,
was used as a second reference (δ -97.35 ppm) and to optimize
Hartmann-Hahn CP matching conditions. 29Si MAS NMR
spectra were recorded on a UNITYplus-500 spectrometer.
Mass spectra were obtained on a Finnigan MAT 8230 spec-
The ready commercial availability of Ti(OPri)4 and
Ph2Si(OH)2 and their simple conversion into TiO2 and
the organosiloxanol 1 make the latter compound a
potential precursor for further tailor-made polydiphen-
ylsiloxane derivatives.
(15) (a) Puff, H.; Schuh, W.; Sievers, R.; Wald, W.; Zimmer, R. J .
Organomet. Chem. 1984, 260, 271. (b) Gmelin Handbook of Inorganic
Chemistry, 8th ed.; Springer-Verlag: Berlin, 1986; Part 13, p 10.

Model Compounds for Diphenylsiloxane Polymer
Organometallics, Vol. 18, No. 12, 1999 2329
Ta ble 2. Selected Bon d Len gth s [Å], An gles [d eg],
a n d Tor sion An gles [d eg] for 1 a n d 2
trometer. Ions showed the expected isotopic pattern. The
elemental analyses were performed on an instrument from
Carlo Erba Strumentazione (model 1106). The densities of
single crystals were determined using a Micromeritics Accu
Pyc 1330. The molecular weight measurements were per-
formed on a Knaur osmometer.
1 (X ) H)a
2 (X ) Sn)b
Si(1)-O(3)
Si(1)-O(2)
Si(1)-C(1)
Si(1)-C(11)
Si(2)-O(2)
Si(2)-O(1)
Si(2)-C(21)
Si(2)-C(31)
O(1)-X(1)
1.6064(6)
1.609(2)
1.853(2)
1.853(2)
1.609(2)
1.627(2)
1.854(2)
1.856(2)
0.70(4)
1.602(1)
1.598(3)
1.845(4)
1.835(4)
1.603(3)
1.591(3)
1.851(5)
1.861(5)
1.970(3)
2.129(6)
2.116(6)
2.130(7)
1,1,3,3,5,5,7,7-Oct a p h en yl-1,3,5,7-t et r a siloxa n e-1,7-d i-
ol (1). spiro-Ti[(OSiPh2)4O]2 (10.0 g, 6.0 mmol) was dissolved
in 250 mL of THF, and H2O (1.10 g, 60 mmol) was added. After
stirring for 6 h the layers were separated and the organic layer
was removed in vacuo. The solid residue was recrystallized
from toluene, resulting in 4.2 g (86%) of 1 as colorless
crystalline solid, mp 132 °C. 1H NMR δ: 7.38 (complex pattern,
Ph), 7,26 (complex pattern, Ph), 7.10 (complex pattern, Ph).
13C{1H} NMR δ: 134.5 (Ci), 134.4 (Co), 134.3 (Ci, Co super-
imposed), 130.1 (Cp), 130.08 (Cp), 127.7 (Cm). 29Si{1H} NMR δ:
-36.9 (OSi(OH)Ph2), -45.3 (OSiPh2O). 29Si{1H} MAS NMR
δ: -39.7 (OSi(OH)Ph2), -47.8 (OSiPh2O). MS m/z (%): 791
(25) [M+], 714 (27) [M+ - Ph], 636 (65) [M+ - 2 Ph], 593 (38)
[M+ - OSiPh2], 558 (94) [M+ - 3 Ph]. Anal. Calcd for C48H42O4-
Si4 (795.21): C, 72.50; H, 5.32. Found: C, 70.97; H, 5.34. IR
(KBr): 3591 (m, νOH), 3070 (m), 3020 (m), 1958 (m), 1899 (m),
1827 (m), 1590 (s), 1486 (s), 1428 (s), 1309 (w), 1264 (w).
Sn(1)-C(41)
Sn(1)-C(51)
Sn(1)-C(61)
O(3)-Si(1)-O(2)
O(3)-Si(1)-C(1)
O(2)-Si(1)-C(1)
O(3)-Si(1)-C(11)
O(2)-Si(1)-C(11)
C(1)-Si(1)-C(11)
O(2)-Si(2)-O(1)
O(2)-Si(2)-C(21)
O(1)-Si(2)-C(21)
O(2)-Si(2)-C(31)
O(1)-Si(2)-C(31)
C(21)-Si(2)-C(31)
Si(1)-O(2)-Si(2)
Si(1a)-O(3)-Si(1)
Si(2)-O(1)-X(1)
O(1)-Sn(1)-C(51)
O(1)-Sn(1)-C(41)
C(51)-Sn(1)-C(41)
O(1)-Sn(1)-C(61)
C(51)-Sn(1)-C(61)
C(41)-Sn(1)-C(61)
109.07(7)
108.80(7)
109.96(9)
108.41(7)
109.37(9)
111.18(9)
111.0(1)
108.34(9)
110.5(1)
108.71(9)
106.0(1)
112.35(9)
167.6(1)
180.00(3)
117(3)
108.8(1)
109.9(2)
107.7(2)
109.0(2)
111.3(2)
110.9(2)
112.0(2)
108.7(2)
108.1(2)
105.1(2)
111.7(2)
111.3(2)
166.1(2)
180.00(7)
145.6(2)
103.4(2)
101.6(2)
117.0(4)
106.2(2)
113.9(3)
112.8(4)
1,1,3,3,5,5,7,7-Oct a p h en yl-1,7-t r icycloh exylst a n n yl-
1,3,5,7-tetr a siloxa n e (2). H(OSiPh2)4OH (1) (0.5 g, 0.62
mmol) was dissolved in 60 mL of toluene, and cyclo-Hex3SnOH
(0.47 g, 1.23 mmol) was added. After heating at a Dean and
Stark condenser for 8 h, the solvent was evaporated. Recrys-
tallization of the residue from CH2Cl2/hexane provided 0.62 g
(87%) of 2 as a colorless crystalline solid, mp 156 °C. 1H NMR
δ: 7.33 (complex pattern, Ph), 7.15 (complex pattern, Ph), 6.98
(complex pattern, Ph), 1.30 (complex pattern, cyclo-Hex). 13C-
{1H} NMR δ: 138.5 (Ci), 135.7 (Ci), 134.7 (Co), 134.6 (Co), 129.2
(Cp), 128.7 (Cp), 127.1 (Cm), 127.08 (Cm), 33.0 (1J (13C-119Sn)
342 Hz, Sn-CH), 30.9 (2J (13C-117/119Sn) 14 Hz, CHCH2), 28.8
(3J (13C-117/119Sn) 64 Hz CHCH2CH2), 26.8. 29Si{1H} NMR δ:
-45.8 (2J (29Si-O-119Sn 70 Hz, Si-O-Sn), -47.7 (OSiPh2O).
119Sn{1H} NMR δ: -7.9. 29Si{1H} MAS NMR δ: -46.2
(Si-O-Sn), -46.8 (OSiPh2O).
O(1)-Si(2)-O(2)-Si(1)
O(3)-Si(1)-O(2)-Si(2)
O(2)-Si(1)-O(3)-Si(1a)
O(2)-Si(2)-O(1)-Sn(1)
-7.9(5)
-174.9(5)
63(13)
69.7(10)
107.6(10)
-86(17)
74.5(4)
a
b
a ) -x+1, -y+1, -z (1). a ) -x,-y, -z (2).
715 (s), 698 (s), 523 (s), 508 (s), 384 (m) cm-1. MW (10 mg/mL
in CHCl3): 940 g/mol.
MS m/z (%): 867 (23) [M+ - 4 Ph, -Sn-cyclo-Hex3], 714
(16) [M+ - 6 Ph, -Sn-cyclo-Hex3], 653 (30) [M+ - 4 Ph, -Sn-
cyclo-Hex3, -OSiPh2], 637 (36) [M+ - 4 Ph, -Sn-cyclo-Hex3,
-O2SiPh2], 594 (40) [M+ - 2 Ph, -Sn-cyclo-Hex3, -O2SiPh2,
-OSiPh2]. Anal. Calcd for C84H106O5Si4Sn2 (1545.58): C, 65.28;
H, 6.91. Found: C, 64.98; H, 7.11. IR (KBr): 3067 (m), 3049
(m), 3021 (m), 2916 (s), 2845 (s), 1591 (m), 1487 (w), 1445 (s),
1428 (s), 1262(m), 1127 (s), 1073 (s), 984 (s), 877 (m), 840 (m),
Cr ysta llogr a p h y. Crystals of H(OSiPh2)4OH (1) and (cyclo-
Hex3SnOSiPh2OSiPh2)2O (2) were grown from
a CH2Cl2/
hexane solution. Intensity data for the colorless crystals were
collected on a Nonius Kappa CCD diffractometer with graphite-
monochromated Mo KR radiation at 291 K. The data collec-
tions covered almost the whole sphere of reciprocal space with
360 frames via ω-rotation (∆/ω ) 1°) at two times 20 s (1, 2)
per frame. The crystal-to-detector distance was 2.7 cm (1) and
2.9 cm (2). Crystal decay was monitored by repeating the
initial frames at the end of data collection. Analyzing the
duplicate reflections, there was no indication for any decay
(1, 2). The data were not corrected for absorption effects. The
structures were solved by direct methods SHELXS9716a and
successive difference Fourier syntheses. Refinement applied
full-matrix least-squares methods with SHELXL97.16b
H atoms for 1 were located in the difference Fourier map
and refined isotropically. The H atoms for 2 were placed in
geometrically calculated positions using a riding model. For
the phenyl groups they were refined with a common isotropic
temperature factor (Haryl C-H 0.93 Å, Uiso 0.110(4) Å2), and
for the cyclohexyl groups the atomic displacement parameters
were fixed to 1.5 times those of the C atoms (C-Hsec 0.97 Å).
Disordered cyclohexyl groups were found for 2 (C(42), C(43),
C(44), C(45), C(66), C(42′), C(43′), C(44′), C(45′), C(66′) (sof
0,5)).
803 (m), 740 (s), 716 (s), 698 (s), 519 (s), 485 (s), 418 (m) cm-1
.
1,1-Di-ter t-bu tyl-3,5,7,9-octaph en yl-2,4,6,8,10-pen taoxa-
3,5,7,9-t et r a sila -1-st a n n a cyclod od eca n e, cyclo-t-Bu 2Sn -
(OSiP h 2OSiP h 2)2O (3). H(OSiPh2)4OH (1) (1.25 g, 1.50 mmol)
and (t-Bu2SnO)3 (0.38 g, 1.50 mmol) were dissolved in 100 mL
of CHCl3. The reaction mixture was heated at reflux for 4 h.
Evaporation of the solvent provided 1.19 g (74%) of 3 as a
colorless amorphous solid, mp >250 °C. 1H NMR δ: 0.96
(3J (1H-119Sn) 104 Hz, CCH3), 7.05 (complex pattern, Ph), 7.21
(complex pattern, Ph), 7.34 (complex pattern, Ph), 7.44 (com-
plex pattern, Ph). 13C{1H} NMR δ: -29.2 (CCH3), -39.9
(1J (13C-119Sn) 499 Hz, CCH3), 137.8 (Ci), 135.4 (Ci) 134.6 (Co),
129.5 (Cp), 129.2 (Cp), 127.4 (Cm). 29Si{1H} NMR δ: -44.9 (2J -
(29Si-117/119Sn) 69 Hz, OPh2Si-O-Sn), -47.4 (OPh2Si-O-Si).
119Sn{1H} NMR δ: -158.0 (2J (119Sn-O-29Si) 69 Hz. 29Si{1H}
MAS NMR δ: -44.7, -47.4, -49.1-50.2. 119Sn{1H} MAS NMR
δ: -141.2. MS m/z (%): 850 (55) [M+ - 2 t-Bu, -Ph], 653 (56)
(M+ - 2 t-Bu, -Ph, -OSiPh2], 637 (10) [M+ - 2 t-Bu, -Ph,
-O2SiPh2], 533 (32) [M+ - Snt-Bu2, -OSiPh2, -2 Ph], 455 (72)
[ M+ - 2 t-Bu, -Ph, -2 OSiPh2]. Anal. Calcd for C56H58O5Si4-
Sn (1042.16): C, 64.54; H, 5.61. Found: C,64.08; H, 5.71. IR
(KBr): 3068 (m), 3047 (m), 2921 (w), 2850 (m), 2361 (w), 2338
(w), 1591 (w), 1466 (w), 1429 (s), 1124 (s), 966 (s), 741 (m),
(16) (a) Sheldrick, G. M. Acta Crystallogr. 1990 A46, 467-473. (b)
Sheldrick, G. M. University of Go¨ttingen, 1997. (c) International Tables
for Crystallography, Kluwer Academic Publishers: Dordrecht, 1992;
Vol. C. (d) Sheldrick, G. M. SHELXTL-Plus, Release 4.1; Siemens
Analytical X-ray Instruments Inc.: Madison, WI, 1991.

2330 Organometallics, Vol. 18, No. 12, 1999
Beckmann et al.
Atomic scattering factors for neutral atoms and real and
Su p p or tin g In for m a tion Ava ila ble: Tables of all coor-
dinates, anisotropic displacement parameters, and geometric
data for compounds 1 and 2. This material is available free of
charge via the Internet at http://pubs.acs.org.
imaginary dispersion terms were taken from reference16c
.
Figures were created by SHELXTL-Plus.16d Crystallographic
data are given in Table 1; selected bond lengths [Å] and angles
[deg] are listed in Table 2.
Ack n ow led gm en t. We thank the Deutsche Fors-
chungsgemeinschaft and the Fonds der Chemischen
Industrie for financial support.
OM990107Z