9,10-Dimetallatriptycenes of group 14: A structural study

Article abstract of DOI:10.1016/S0022-328X(97)00237-4

From ortho-phenylenemagnesium (1), 9-phenyl-9-germa-10-silatriptycene (5) was prepared via a simple one pot procedure. The previously prepared 9-methyl-10-phenyl-9,10-digermatriptycene (4) and 5 are the first germanium-containing 9,10-dimetallatriptycenes to be structurally characterised. The availability of these structural data allows a comparative discussion of 9,10-dimetallatriptycenes of Group 14.

Full text of DOI:10.1016/S0022-328X(97)00237-4

Ž
.
Journal of Organometallic Chemistry 550 1998 347–353
1
9,10-Dimetallatriptycenes of group 14: a structural study
a
a
a,)
Matheus A. Dam , Franciscus J.J. de Kanter , Friedrich Bickelhaupt
,
b
b
c
c
Wilberth J.J. Smeets , Anthony L. Spek , Jorge Fornies-Camer , Christine Cardin
a
Scheikundig Laboratorium, Vrije UniÕersiteit, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands
b
BijÕoet Center for Biomolecular Research, Vakgroep Kristal- en Structuurchemie, Utrecht UniÕersity, Padualaan 8, NL-3584 CH Utrecht, The
Netherlands
c
Chemistry Department, UniÕersity of Reading, Whiteknights, Reading RG4 9BB, UK
Received 20 March 1997
Abstract
Ž .
Ž .
From ortho-phenylenemagnesium 1 , 9-phenyl-9-germa-10-silatriptycene 5 was prepared via a simple one pot procedure. The
Ž .
previously prepared 9-methyl-10-phenyl-9,10-digermatriptycene 4 and 5 are the first germanium-containing 9,10-dimetallatriptycenes to
be structurally characterised. The availability of these structural data allows a comparative discussion of 9,10-dimetallatriptycenes of
Group 14. q 1998 Elsevier Science B.V.
Keywords: Silicon; Germanium; Tin; 9,10-Dimetallatriptycenes; ortho-Phenylenemagnesium
1. Introduction
illustrated by the synthesis of 9-phenyl-9-germa-10-
silatriptycene 5 .
Ž .
Recently, we reported a novel synthetic application
of the bifunctional organomagnesium compound ortho-
Ž . w x
phenylenemagnesium 1 1 , via which 9,10-dimetal-
2. Results and discussion
w x
latriptycenes of group 14 are readily accessible 2 :
( )
2.1. Synthesis of 9-phenyl-9-germa-10-silatriptycene 5
reaction of 1 with methyl substituted metal trihalides
furnished new 9,10-dimethyl-9,10-dimetallatriptycenes
1
2
Ž
. Ž
.
3: M sM sSi, Ge or Sn Scheme 1 . The reaction
Treatment of
trichlorophenylgermane, followed by the addition of
trichlorosilane, furnished 5 Scheme 2 , which, after
elution over silica gel and recrystallisation from toluene
was isolated in 76% yield.
1
at y158C in THF with
could even be tuned to furnish the unsymmetrically
substituted 9-methyl-10-phenyl-9,10-digermatriptycene
Ž
.
1
2
1
2
Ž
.
R s Ph, R s Me, M s M s Ge . This was
4
achieved by the reaction of three equivalents of 1 with
one equivalent of trichlorophenylgermane and transfor-
mation of the selectively formed tri-Grignard reagent 2
2.2. X-ray crystal structures of 9-methyl-10-phenyl-
1
1
Ž
.
( )
R s Ph, M s Ge with one equivalent of
9,10-digermatriptycene 4 and 10-phenyl-10-germa-9-
( )
trichloromethylgermane to 4.
silatriptycene 5
In principle, this stepwise one pot approach may give
access to a large variety of 9,10-dimetallatriptycenes
with different metals and different substituents. This is
Single crystals of 5 suitable for X-ray crystal struc-
ture determination were obtained upon slow diffusion of
n-hexane from the gas phase into a toluene solution of
5. Similarly, we were able to obtain the crystal structure
of 4; the availability of three structures of 9,10-dimetal-
latriptycenes of Group 14, that is, that of 4, 5, and the
)
Corresponding author. Tel.: q31 20 4447479. Fax: q31 20
w x
previously determined structure of 3c 2 , together with
4447488. E-mail: bickelhpt@chem.vu.nl.
1 Dedicated to Prof. Dr. K. Wade at the occasion of his 65th
birthday in friendship and appreciation.
the reported structure of 9-hydroxy-10-methyl-9,10-dis-
1
2
1
2
Ž
. w x
ilatriptycene 6 M sM sSi, R sMe, R sOH 3 ,
0022-328Xr98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

(
)
348
M.A. Dam et al.rJournal of Organometallic Chemistry 550 1998 347–353
Scheme 1. Synthesis of substituted 9,10-dimetallatriptycenes 3 and 4.
allows a comparative discussion of this novel class of
compounds.
The solid state structures of 4 and 5 are depicted in
Figs. 1 and 2, respectively. Crystal data, data collection,
and refinement parameters are reported in Table 1.
Fractional atomic coordinates and equivalent thermal
parameters of 4 and 5 are presented in Tables 2 and 3,
respectively. Selected bond distances and bond angles
of 4 and 5, together with the corresponding values for
3c and 6, are listed in Table 4.
Fig. 1. ORTEP plot of 4 with ellipsoids drawn at 30% probability
level.
triptycene skeleton imposes substantial ring strain be-
cause, for purely geometric reasons, this arrangement
does not simultaneously allow perfectly tetrahedral an-
Fig. 1 shows that in 4, the phenyl substituent is
disordered over two orientations with respect to the
triptycene skeleton; the two orientations are represented
Ž
.
gles around the bridgehead atoms as109.48 and
perfectly trigonal angles around the ipso-carbon atoms
bsgs1208 . For example, when a is artificially
Ž
.
Ž .
Ž
.
Ž
.
Ž
.
by C 8 -C 13 and C 81 -C 131 . These orientations are
populated in a 1:1 ratio and they probably result from
packing effects. Pairs of molecules of 4 pack together,
each with its own disordered phenyl group orientation
fixed at 109.48, the triptycene skeleton can only be
formed with bs109.58 and gs130.58. Similarly, when
b and g are kept at 1208, a necessarily has to decrease
to 97.28. Not surprisingly, the ‘real’ molecules choose a
compromise between the two extremes.
to avoid collision. In the H and 13C NMR spectra of
1
Ž
.
both 4 and 5 Tol-d8: 298–198 K , only one set of
signals is observed for the phenyl substituent, indicating
that in solution there is no hindered rotation around the
The geometric restrictions imposed on the bond an-
gles lead to a change in the rehybridisation of the
orbitals concerned and this, in turn, has consequences
for the bond lengths: in comparison to ideal sp3 hybridi-
sation, the metal uses more p character in the bridge-
head–phenylene bonds in order to make a smaller than
109.48, and thus more s character is left for the bridge-
Ž
.
Ž
Ge–C phenyl axis.
.
It appears Table 4 that 4 and 5 are strained and
have some general structural features in common. In
Ž
both 4 and 5 the average ‘internal’ angles bn bn s
Ž . . Ž Ž .
M n -Ci pso-Ci pso; see Fig. 3 4: b1 s116.1 5 8, b2 s
Ž . Ž . Ž . .
115.0 5 8, 5: b1 s116.1 5 8, b2 s114.3 5 8 are smaller
Ž .
Ž
and the average ‘external angles’ gn gn sM n -Ci pso-C:
. Ž Ž . Ž .
Fig. 3 4: g1 s124.8 5 8, g2 s125.6 5 8, 5: g1 s
Ž . Ž . .
125.7 7 8, g2 s125.7 7 8 are wider than the standard
Ž
angle of 1208. The average angles an an sCi pso
-
Ž . . Ž Ž . Ž .
M n -Ci pso 4: a1 s102.5 4 8, a2 s102.9 3 8, 5: a1
Ž .
Ž . .
s104.6 5 8, a2 s101.8 4 8 are more acute than
109.58, the ideal angle for sp3 hybridised bridgehead
atoms. These structural deformations indicate that the
Fig. 2. ORTEP plot of 5 with ellipsoids drawn at 30% probability
Scheme 2. Synthesis of 10-phenyl-10-germa-9-silatriptycene 5.
level.

(
)
M.A. Dam et al.rJournal of Organometallic Chemistry 550 1998 347–353
349
Table 1
Crystal data, data collection, and refinement parameters for the 9,10-dimetallatriptycenes 4 and 5
4
5
Crystal data
Formula
C25 H20Ge2
465.65
monoclinic
C24 H18GeSi
407.06
orthorhombic
Molecular weight
Crystal system
Space group
Ž
.
Ž
.
P21rc No. 14
P212121 No. 19
Ž .
10.679 5
˚
Ž .
a A
Ž .
11.889 4
˚
Ž .
b A
Ž .
10.054 5
Ž .
12.082 5
˚
Ž .
c A
Ž .
99.36 4
Ž .
2054 2
Ž .
17.417 9
Ž .
14.942 6
90
Ž .
b 8
3
˚
Ž
.
V A
Z
1927.9
4
4
y3
Ž
.
Ž .
1.506 1
936
Dcalc g cm
F 000
1.402
832
16.6
Ž
.
y1
Ž
.
m cm
Crystal size mm
Data collection and refinement
29.3
Ž
.
0.20=0.25=0.30
0.30=0.20=0.20
Ž .
umin, umax
Radiation
Monochromator
Temp. K
150
293
1.19, 25.00
MoK a
graphite
3.37, 25.91
MoK a
graphite
˚
Ž .
l A
0.71073
0.71073
–
–
–
h 0:13; k 0:14; l 0:17
13338
Ž .
Dv 8
0.99q0.35 tanu
Ž
.
Hor. and vert. aperture mm
Reference reflections
Data set
3.00q1.50 tanu, 4.00
2-1-7, 2-2-1, 5-2-2
h y10:14; k y11:0; l y20:20
4459
Total data
Total unique data
No. refined parameters
Weighting schemea
Final R1b
3612
312
2034
258
as0.0646, bs4.48
0.0590
0.1429
1.042
as0.0590, bs1.35
0.0407
0.1175
1.156
–
wR2c
Sd
Ž
.
Ž
.
and Drs
max
Drs
in final cycle
0.000, 0.001
av
a
b
c
d
2
2
w
2Ž
.
Ž
.
x
Weighting schemes1r s Fo q a)P qb)P .
w Ž<<
<
<
<<.
<
<x
R1s Ý Fo y Fc rÝ Fo .
2
0.5
w w Ž
wR2s Ý w Fo yFc
2 .2 x w Ž 2 .2 x
rÝ w Fo
.
2
0.5
w w Ž
Ss Ý w Fo yFc
2 .2 x Ž
.x
r nyp .
˚
Ž
Ž .
s 1.954 5
w x
Ž . w x
head–substituent bonds. Consequently the bridgehead–
substituent bonds of the 9,10-dimetallatriptycenes 4 and
5 will be shortened while the bridgehead–phenylene
bonds will be stretched in comparison to those of
unstrained model compounds, as has been observed for
pounds Ge-C
A
Ž .
4 , 1.954 1 6 ,
w x
w x i pso
Ž
.
˚
˚
˚
Ž .
1.948 4 A 7 ; Si-Ci pso s1.85 1 A 5 , 1.852 13 A
w x
.
8 . In the case of 4, the differences are within the
range of the experimental error, but the trend observed
is consistent. In this context it has to be noted that the
observed elongation of the bridgehead–phenylene bonds
is expected to be less pronounced than the shortening of
the bridgehead–substituent bonds because, per bridge-
head atom, the total amount of reduced s character is
spread over three bridgehead–phenylene bonds while
the identical amount of enhanced s character appears in
only one bridgehead–substituent bond.
w x
all-carbon triptycenes 9 . For example, the
Ž
Ž . Ž .
bridgehead–substituent bonds in 4 and 5 4: Ge 1 -C 1
˚
Ž
˚
Ž .
Ž .
˚
Ž
.
Ž .
Ž .
s1.938 7 A, Ge 2 -C 8r81 s1.94 2 A; 5: Si 1 -
˚
.
Ž .
.
Ž . Ž .
Ž .
H 1 s1.468 39 A, Ge 2 -C 8 s1.944 4 A are rela-
tively short when compared to those in unstrained com-
Ž
pounds with analogous substitution patterns Ge-
˚
˚
Ž
.
.
Ž .
w x
Ž
.
w x
C methyl s1.951 8 A 4 ; Si-Hs1.491 28 A 5 ;
˚
Ž
Ž . w x
Ž . w x
.
w x
Ge-C aryl s1.954 1 6 , 1.948 4 A 7 . On the other
Generally speaking, the 9,10-disilatriptycene 6 3
and the 9,10-distannatriptycene 3c 2 show similar
trends to 4. For example, all three compounds have
relatively short M–R bonds and relatively long M–Ci pso
bonds, the angles a and b are more acute than 109.48
Ž
w x
hand, the average bridgehead–phenylene bonds 4:
˚
˚
Ž .
Ž .
Ž .
Ž .
Ž .
Ge 1 -Ci pso s1.952 7 A, Ge 2 -Ci pso s1.956 7 A; 5:
˚
˚
.
Ž .
Ž .
Ž .
Si 1 -Ci pso s1.869 8 A, Ge 2 -Ci pso s1.961 6 A are
slightly longer than those in unstrained model com-

(
)
350
M.A. Dam et al.rJournal of Organometallic Chemistry 550 1998 347–353
Table 2
Table 3
Fractional atomic coordinates and equivalent thermal parameters of 4
Fractional atomic coordinates and equivalent thermal parameters of 5
with estimated standard deviations in parentheses
with estimated standard deviations in parentheses
Atom
x
y
z
Ueaq
˚
Ž
A
Atom
x
y
z
Ueaq
˚
Ž
A
2
2
.
.
Ž .
Ge 2
Ž .
0.56816 6
0.79098 6
Ž .
0.60153 7
0.48361 7
Ž .
0.20726 4
0.16540 5
Ž .
0.0234 2
0.0254 3
Ž .
Ge 2
Ž .
0.7504 3
0.7502 1
Ž .
0.3401 1
0.5609 1
Ž .
0.0523 1
Ž .
0.044 1
0.038 1
Ge 1
Ž .
Si 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
0.1507 1
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
.
Ž
.
.
Ž
.
Ž
.
C 1
0.4275 6
0.6750 7
0.2317 5
0.034 3
H 1
0.7418 64
0.2323 33
0.0047 28
0.035 11
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
C 2
0.5494 6
0.4641 7
0.1281 4
0.025 2
C 2
0.8859 7
0.4332 10
0.0265 6
0.046 2
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
C 3
0.6498 6
0.4103 6
0.1075 4
0.024 2
C 3
0.8928 8
0.5327 8
0.0682 6
0.042 2
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
.
.
.
.
Ž .
Ž .
C 4
0.6437 6
0.3138 7
0.0499 4
0.029 2
C 4
0.9857 6
0.6087 10
0.0473 9
0.056 3
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
C 5
0.5380 7
0.2668 7
0.0140 4
0.032 2
C 5
1.0710 8
0.5843 13
y0.0191 9
0.075 4
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž
.
.
Ž
Ž
.
Ž .
C 6
0.4393 6
0.3183 7
0.0339 4
0.029 2
C 6
1.0666 12
0.4850 10
y0.0623 10
0.087 5
Ž .
Ž .
Ž .
Ž .
0.1245 11
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
C 7
0.4451 6
0.4155 7
0.0901 4
0.027 2
C 7
0.9778 7
0.4074 11
y0.0404 8
0.062 3
)
Ž .
Ž .
0.9751 18
Ž .
Ž
.
.
.
.
.
.
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
) C 8
0.927 2
0.409 3
0.023 4
C 8
0.7512 12
0.6990 3
0.2175 3
0.045 1
Ž .
Ž
.
Ž .
Ž
Ž .
Ž .
C 10
Ž .
Ž
.
.
Ž .
Ž .
) C 9
0.299 2
0.1604 12
0.049 5
C 9
Ž
0.8586 9
0.7470 10
0.2448 7
0.069 3
Ž
.
.
.
.
Ž .
Ž .
Ž
Ž .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž
.
.
.
Ž
Ž .
Ž .
) C 10
1.070 3
0.247 4
0.1353 17
0.056 7
0.8707 14
0.8423 11
0.2938 7
0.092 4
Ž
Ž
.
.
.
Ž .
Ž
Ž .
Ž
Ž
Ž .
Ž .
Ž .
) C 11
1.1164 17
0.308 2
0.0797 13
0.055 5
C 11
0.7531 22
0.8922 5
0.3189 5
0.110 3
Ž
Ž
Ž .
Ž
Ž .
Ž
Ž
Ž
.
Ž .
Ž .
) C 12
1.0582 17
0.408 2
0.0392 12
0.063 5
C 12
0.6496 15
0.8474 13
0.2926 8
0.104 5
Ž
Ž
Ž .
Ž
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
C 13
0.9605 18
0.461 2
0.0671 11
0.061 5
C 13
0.6358 9
0.7484 9
0.2416 7
0.070 3
Ž
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
Ž
Ž
.
.
.
.
.
.
Ž .
Ž .
Ž .
C 14
C 15
C 16
C 17
C 18
C 19
C 20
C 21
C 22
C 23
C 24
C 25
0.6704 6
0.5171 7
0.2930 4
0.028 2
C 14
0.7489 11
0.3254 3
0.1760 3
0.041 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ž .
Ž .
0.7698 6
0.4593 7
0.2735 4
0.025 2
C 15
0.7512 11
0.4274 3
0.2244 3
0.040 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ž .
Ž .
0.8462 6
0.3963 7
0.3313 5
0.037 3
C 16
0.7524 11
0.4268 4
0.3174 3
0.049 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ž .
Ž .
0.8259 8
0.3894 9
0.4065 5
0.047 3
C 17
0.7503 11
0.3273 4
0.3638 3
0.058 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ž .
Ž .
0.7318 7
0.4507 8
0.4265 5
0.041 3
C 18
0.7521 14
0.2288 4
0.3185 4
0.057 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž .
Ž .
Ž .
0.6530 7
0.5143 7
0.3695 4
0.033 3
C 19
0.7515 13
0.2284 4
0.2264 3
0.051 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
0.6713 6
0.7299 7
0.1707 4
0.025 2
C 20
0.6126 7
0.4301 9
0.0237 7
0.045 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
0.7731 5
0.6767 7
0.1516 4
0.023 2
C 21
0.6107 7
0.5375 9
0.0696 6
0.043 2
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
0.8497 6
0.7619 7
0.1249 4
0.028 2
C 22
0.5175 8
0.6108 9
0.0483 8
0.058 3
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
.
.
Ž
.
.
.
Ž .
Ž .
0.8282 6
0.8976 8
0.1176 4
0.031 2
C 23
0.4266 11
0.5847 11
y0.0134 9
0.078 4
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž
Ž
Ž .
Ž .
0.7289 7
0.9481 8
0.1369 4
0.037 3
C 24
0.4305 13
0.4843 10
y0.0593 9
0.086 5
Ž
Ž .
Ž .
Ž .
Ž .
Ž
Ž .
Ž
Ž .
Ž .
0.6502 6
0.8641 7
0.1637 4
0.028 2
C 25
0.5243 8
0.4080 10
y0.0381 8
0.062 3
)
Ž
.
.
Ž
.
.
Ž .
Ž
.
.
.
.
.
Ž .
) C 81
0.9329 18
0.411 2
0.1526 12
0.018 5
U
is defined as one third of the trace of the orthogonalized U
i j
Ž
Ž
Ž .
Ž
Ž .
) C 91
0.9443 17
0.285 2
0.1188 13
0.048 6
eq
tensor.
Ž
.
Ž .
Ž .
Ž
Ž .
) C 101 1.048 3
0.229 3
0.1109 17
0.053 7
Ž
.
Ž
.
.
.
Ž .
0.4343 18
Ž
Ž .
) C 111 1.1477 17
0.311 2
0.1327 12
0.047 6
Ž
.
.
Ž
Ž
.
.
Ž
Ž .
) C 121 1.1420 14
0.1617 10
0.045 5
Ž
Ž
Ž
Ž .
Ž .
C 131 1.0362 12
0.4837 15
0.1732 9
0.032 4
and 1208, respectively, and the angles g are larger than
1208. However, careful examination of the angles a, b
and g of 6, 4 and 3c reveals some influence of the
bridgehead atom: deviations of b and g from 1208
aUeq is defined as one third of the trace of the orthogonalized U
tensor.
Indicates site occupation factors0.50.
i j
)
Table 4
Selected bond distances A and bond angles 8 of 9,10-dimetallatriptycenes 3c, 4, 5 and 6 with estimated standard deviations in parentheses see
˚
Ž .
Ž .
Ž
.
Fig. 3
6a
5b
4b
3cc
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
Ž .
M 1 sSi, R 1 sMe
M 2 sSi, R 2 sOH
M 1 sSi, R 1 sH
M 1 sGe, R 1 sMe
M 1 sSn, R 1 sMe
Ž . Ž .
M 2 sSn, R 2 sMe
Ž .
Ž .
Ž . Ž .
Ž . Ž .
M 2 sGe, R 2 sPh
M 2 sGe, R 2 sPh
Ž . Ž .
Ž
.
Ž .
1.94 2
Ž .
M 1 -R 1
Ž . Ž .
1.835
1.636
1.870
1.864
1.468 39
1.938 7
2.113 4
Ž .
2.113 4
Ž .
Ž .d
M 2 -R 2
1.944 4
d
Ž .
Ž .
Ž .
Ž .
2.153 2
M 1 -Ci pso
Ž .
1.869 8
1.952 7
d
Ž .
Ž .
Ž .
2.153 2
M 2 -Ci pso
1.961 6
1.956 7
Ci pso-Cdi pso
1.416
1.42 2
1.41 1
Ž .
Ž .
Ž .
1.405 3
d
d
Ž
Ž .
.
Ž .
Ž .
Ž .
101.42 9
a1 Ci pso-M 1 -Ci pso
103.01
104.23
115.70
113.94
126.08
126.27
104.6 4
Ž .
102.5 4
102.9 3
116.1 5
115.0 5
d
Ž
Ž .
.
Ž .
Ž .
101.42 9
a2 Ci pso-M 1 -Ci pso
b1 M 1 -Ci pso-Ci pso
b2 M 2 -Ci pso -Ci pso
g1 M 1 -Ci pso-C
101.8 4
116.1 5
114.3 5
d
Ž
Ž .
.
Ž .
Ž .
Ž .
117.4 2
Ž
Ž
Ž .
.
.
Ž .
Ž .
Ž .
117.4 2
d
Ž .
.
Ž .
Ž .
Ž .
Ž .
125.7 7
Ž .
124.8 5
Ž .
124.1 2
124.1 2
d
Ž
Ž .
.
g2 M 1 -Ci pso-C
125.7 7
125.6 5
a
w x
From 3 .
b This work.
c
w x
From 2 .
dAverage value.

(
)
M.A. Dam et al.rJournal of Organometallic Chemistry 550 1998 347–353
351
( )
4.1. 9-Phenyl-9-germa-10-sila-triptycene 5
Ž
.
Fig. 4
At y158C, a solution of trichlorophenylgermane
Ž
.
0.350 g; 1.37 mmol in 7.37 ml of toluene was added
during 20 min to a solution of 1 4. 10 mmol of the
formal monomeric unit C6 H4 Mg in 100.0 ml of THF.
Ž
.
Fig. 3. Characteristic angles in the triptycene skeleton.
After additional stirring at y158C for 2 h, trichlorosi-
Ž
.
lane 0.186 g; 1.37 mmol in 20.0 ml of benzene was
added during 45 min. The reaction mixture was stirred
for 2 h at y158C and 1 h at 58C, after which it was
allowed to warm to room temperature overnight. The
mixture was quenched with saturated ammonium chlo-
Ž .
Ž .
Ž
.
decrease from silicon 6 via germanium 4 to tin 3c ,
while deviations of a from 109.48 increase in the same
direction. These observations can be explained by the
difference in hardness between silicon, germanium and
tin. In the case of silicon, which is relatively hard,
deviations from the tetrahedral environment around the
Ž
.
ride solution and extracted with toluene 3=20 ml .
Ž
.
The combined organic layers were dried MgSO4 , fil-
tered and the solvent was evaporated in vacuo. The
residue was dissolved in benzene and eluted from silica.
Evaporation in vacuo of the solvent furnished the
crude product, which was recrystallised from toluene
Ž
.
metal atom are more difficult large a ; this goes at the
expense of a larger deviation in the angles b and g in
order to allow the closure of the triptycene skeleton.
Germanium is softer and allows a larger deformation of
its tetrahedral environment small a . Consequently, to
meet the geometrical requirements, smaller deviations
of the angles b and g at the benzene rings are feasible.
For tin, which is softer than germanium, these trends are
even more pronounced.
Ž
.
Ž
.
2= to yield 5 as colourless crystals. Yield: 0.423 g
Ž
.
76% ; mp: )2608C.
1
3
Ž
.
Ž
.
Ž
Ž
.
H NMR 400 MHz, CDCl3 : ds7.96 m, J H,H
4
4
Ž
.
Ž
.
s 7.5 Hz, J H,H s 1.4 Hz, J H,H s 1.3 Hz,
5
3
Ž
.
Ž
..
Ž
Ž
.
J H,H s0.7 Hz, 2H; H 18 , 7.79 dq, J H,H s7.2
4
5
Ž
.
Ž
.
Hz, J H,H s 1.3 Hz, J H,H s 0.8 Hz, 3H;
3
4
Ž
..
Ž
Ž
.
Ž
.
H 4,5,16 , 7.72 bm, J H,H s7.3 Hz, J H,H s1.2
5
5
Ž
..
.
Ž
.
Hz, J H,H s 0.8 Hz, J H,H s 0.5 Hz, 3H;
3
4
Ž
Ž
Ž
.
Ž
.
H 1,8,13 , 7.33 m, J H,H s7.5 Hz, J H,H s1.4
3
3
Ž
..
Ž
Ž
.
5
Ž
.
Hz, 1H; H 20 , 7.32 m, J H,H s7.6 Hz, J H,H s
3. Conclusions
4
Ž
.
Ž
.
3
7.5 Hz, J H,H s1.3 Hz, J H,H s0.7 Hz, 2H;
3
Ž
..
Ž
Ž
.
Ž
Ž
.
3
H 19 , 7.06 m, J H,H s7.6 Hz, J H,H s7.2 Hz,
The synthesis of 9-phenyl-9-germa-10-silatriptycene
5 demonstrates that our synthetic approach towards
4
Ž
.
..
Ž
Ž
Ž
.
J H,H s1.2 Hz, 3H; H 3,6,15 , 7.02 m, J H,H s
Ž .
3
4
Ž
.
Ž
.
7.6 Hz, J H,H s7.3 Hz, J H,H s1.3 Hz, 3H;
9,10-dimetallatriptycenes is quite versatile. The avail-
ability of the crystal structures of 5 and 4 allowed a
comparative study of 9,10-dimetallatriptycenes of Group
14, which furnished a consistent interpretation of the
specific bonding situation at the bridgehead position of
these species.
1
Ž
..
Ž
.
Ž
..
H 2,7,14 , 5.67 bs, J Si,H s214.7 Hz, 1H; H 10 ;
13C NMR 100 MHz, C6 D6 : d s 148.2 m;
Ž
.
Ž
1
3
Ž
..
Ž
Ž
.
Ž
.
C 8a,9a,12 , 142.1 dq, J C,Si s67.0 Hz, J C,H s
2
Ž
.
Ž
..
Ž
Ž
6.9 Hz, J C,H s4.4 Hz; C 4a,10a,11 , 136.5 dm,
1
1
Ž
.
Ž
..
Ž
.
1
J C,H s160.9 Hz; C 18 , 134.3 dd, J C,H s165.6
3
Ž
.
Ž
..
Ž
Ž
.
Ž
Hz, J C,H s7.0 Hz; C 4,5,16 , 132.3 dd, J C,H s
3
Ž
.
Ž
..
165.3 Hz, J C,H s6.1 Hz; C 1,8,13 , 130.3 dt,
1
3
Ž
.
Ž
.
Ž
..
J C,H s160.1 Hz, J C,H s7.6 Hz; C 20 , 129.3
1
2
4. Experimental
Ž
Ž
.
Ž
Ž
.
Ž
Ž
..
.
dd, J C,H s168.1 Hz, J C,H s5.4 Hz; C 19 ,
2
1
Ž
Ž
.
Ž
..
Ž
128.5 t, J C,H s3.5 Hz; C 17 , 128.0 dd, J C,H
3
.
Ž
..
Ž
Reactions were performed in fully sealed glassware
using standard high vacuum techniques. 1 and 4 were
s158.8 Hz, J C,H s5.2 Hz; C 2,7,14 , 127.6 dd,
w
x
prepared according to literature 1,2 . Metal trihalides
were commercially purchased. Solvents were dried by
distillation from liquid NarK alloy after pre-drying on
NaOH. NMR spectra were measured at 258C on a
Bruker MSL 400 spectrometer 1H NMR: 400.1 MHz:
Ž
13
1
1
C NMR: 100.6 MHz . 13C, H COSY and H NOE
.
experiments were used for spectral assignment. HRMS
measurements were performed on a Finnigan MAT 90
Ž
.
mass spectrometer direct inlet . Melting points are
uncorrected. Elemental analysis was carried out at the
Mikroanalytisches Labor Pascher, Remagen, Germany.
Ž
Fig. 4. Numbering of 10-phenyl-10-germa-9-silatriptycene 5 s10-
X
X
w
x
phenyl-9,10-dihydro-10-germa-9-sila-9,10 1 ,2 -benzenoanthracene
w
x.
according to IUPAC 10 .

(
)
352
1
M.A. Dam et al.rJournal of Organometallic Chemistry 550 1998 347–353
3
Ž
.
Ž
.
Ž
..
70
J C,H s158.2 Hz, J C,H s6.8 Hz; C 3,6,15 ;
temperature on a Mar Research image plate scanner,
graphite-monochromated Mo–K a radiation used to
measure 95 28 frames, 180 sec. per frame.
28
Ž
HRMS: mrzs404.0420 Calc. for C24 H18 Si Ge
q
Ž
Ž
.
.
M
: mrzs404.0421 . Anal. Calc. for C24 H18GeSi
.
w
x
407.1 : C, 70.81; H, 4.46. Found: C, 70.55; H, 4.41.
XDS package 16 was used to give 2034 unique
Ž
.
reflections merging Rs0.0250 . The heavy atoms were
w
x
4.2. X-ray structure determinations
found from the Patterson map using the SHELX90 17
program and refined subsequently from successive dif-
w
x
4.2.1. X-ray crystallographic analysis of 4
ference Fourier maps using SHELXL 18 , by full-ma-
trix least-squares of 258 variables, to a final R factor of
A colourless block-shaped crystal was mounted on
Ž
.
w
x
Ž
.
top of a glass fibre using the inert oil technique and
transferred to the cold nitrogen stream of an Enraf-Non-
ius CAD4T diffractometer for data collection at 150 K
0.0407 for 2025 reflections with Fo )4s Fo . All
atoms were revealed by the Fourier map difference
Ž .
including H 1 . Non hydrogen atoms were refined
Ž
Rotating anode, 60 kV, 100 mA, graphite-monochro-
anisotropically. Aromatic hydrogen atoms were placed
geometrically and then refined with fixed isotropic
atomic displacement parameter. The weighting scheme
.
mated MoK a radiation, v-scan mode . Unit cell pa-
rameters were determined from a least-squares treat-
ment of the SET4 setting angles of 25 reflections with
10.00-u-13.778. The unit cell parameters were
checked for the presence of higher lattice symmetry
2
2
w
2Ž
.
.
Ž
.
.
Ž
.
w s 1r s Fo q a = P q b = P where P s
2
2
Ž
Ž
.
Max Fo , 0 q2Fc r3, as0.0590 and bs1.35 with
Ž
s Fo from counting statistics gave satisfactory agree-
w
x
11 . A total of 4459 reflections were collected and
ment analyses. Data collection parameters including R1
Fo )4s Fo and wR2 all data values are summa-
rized in Table 1. Full details may be obtained from one
Ž
w
x
Ž
..
Ž
.
merged into a data set of 3612 unique reflections. The
crystals showed broad reflection profiles and reflected
rather poorly. Three intensity control reflections, moni-
tored every hour, showed a decay of 2.6% during the
16.8 h of X-ray exposure time. The structure was solved
Ž
.
of the authors C.C. .
Acknowledgements
Ž
w x.
with direct methods SHELXS86 12 and subsequent
Ž .
Ž
.
difference Fourier analyses. The C 8 –C 13 phenyl
ring is disordered over two orientations in a 1:1 ratio.
Refinement on F2 with all unique reflections was car-
ried out by full matrix least-squares techniques. Hydro-
gen atoms were introduced on calculated positions and
included in the refinement riding on their carrier atoms.
All non-H atoms were refined with anisotropic thermal
parameters; H atoms with isotropic thermal parameters
related to the Ueq of the carrier atoms.
Ž
This work was supported in part M.A.D., W.J.J.S.
and A.L.S. by the Netherlands Foundation for Chemi-
cal Research SON with financial aid from the Nether-
lands Organisation for Scientific Research NWO ,
which is gratefully acknowledged. The cooperation
between the groups in Amsterdam and Reading was
stimulated by the Human Capital and Mobility Pro-
.
Ž
.
Ž
.
Ž
gramme of the European Union Contract No. ER-
.
BCHRXCT930281 .
Weights were introduced in the final refinement cy-
Ž
cles, convergence was reached at R1s0.0590 for 2487
Ž
..
Ž
reflections with Fo)4s Fo , wR2s0.1429 for all
References
.
unique reflections . A final difference Fourier map
shows no features outside the range y0.80:q0.88
w x
1
M.A.G.M. Tinga, G. Schat, O.S. Akkerman, F. Bickelhaupt, E.
Horn, H. Kooijman, W.J.J. Smeets, A.L. Spek, J. Am. Chem.
3
˚
erA .
Ž
.
Crystal data and numerical details of the structure
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w x
2
M.A. Dam, O.S. Akkerman, F.J.J. De Kanter, F. Bickelhaupt,
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Ž
.
N. Veldman, A.L. Spek, Chem. Eur. J. 2 1996 1139.
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3
M. Takahashi, K. Hatano, Y. Kawada, G. Koga, N. Tokitoh, R.
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.
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Neutral atom scattering factors and anomalous dis-
w x
4
O.A. D’yachenko, S.V. Soboleva, L.O. Atovmyan, J. Struc.
w
x
Ž
.
Ž
Ž
.
.
persion factors were taken from 13 . All calculations
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w x
5
w
x
were performed with SHELXL96 14 and the PLATON
w
x
Ž
.
15 package geometrical calculations and illustrations
on a DEC-5000 cluster. Full details may be obtained
Ž
.
Ž
shev, J. Struc. Chem. USSR 15 1974 161 Zh. Struk. Khim. 15
Ž
.
.
1974 170 ; O.A. D’yachenko, L.O. Atovmyan, S.V. Soboleva,
J. Struc. Chem. USSR 16 1975 478 Zh. Struk. Khim. 16
Ž
.
from one of the authors A.L.S. .
Ž
.
Ž
Ž
.
.
1975 505 .
w x
Ž . Ž
.
6
P.C. Chieh, J. Chem. Soc. A , 1971 3241.
4.2.2. X-ray crystallographic analysis of 5
w x
7
M. Charisse, S. Roller, M. Drager, J. Organometal. Chem. 427
´ ¨
Suitable crystals of 5 were grown by slow diffusion
of n-hexane from the gas phase into a solution of the
compound in toluene and mounted on a glass fibre. The
data collection and processing was performed at room
Ž
.
1992 23.
w x
Ž
.
8
J. Allemand, R. Gerdil, Cryst. Struct. Comm. 8 1979 927.
ˆ
w x
9
M. Oki, M. Matsusue, T. Akinaga, Y. Matsumoto, S. Toyota,
Bull. Chem. Soc. Jpn. 67 1994 2831; M. Oki, N. Takiguchi, S.
ˆ
Ž
.

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353
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w
w
x
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Ž
.
1988 4295; F. Imashiro, K. Hirayama, K. Takegoshi, T. Terao,
¨
Ž
.
x
Ž
.
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ˆ
Ž
.
x
Soc. Jpn. 55 1982 159; M. Mikami, K. Toriumi, M. Konno, Y.
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ˆ
Ž
.
Saito, Acta Crystallogr. B31 1975 2474; N. Nogami, M. Oki,
S. Sato, Y. Saito, Bull. Chem. Soc. Jpn. 5 1982 3580.
¨
Ž
.
w
w
w
w
x Ž .
15 A.L. Spek, Acta Crystallogr. A46 1990 C34.
x Ž .
16 W. Kabsch, J. Appl. Crystallogr. 26 1993 795.
17 G.M. Sheldrick, Acta Crystallogr. A46 1990 467.
w
w
x
10 J. Rigaudy, S.P. Klesney, IUPAC Nomenclature of Organic
x
Ž
.
Chemistry, Pergamon, Oxford, 1979, p. 35.
x
Ž
.
x Ž .
11 A.L. Spek, J. Appl. Crystallogr. 21 1988 578.
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