9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)-germatranes. Synthesis, Characterisation, and Crystal Structures

Article abstract of DOI:10.1515/znb-1998-1101

9-Trimethylsilyl- and 9-trimethylgermyl substituted derivatives of 1-(9-fluorenyl)germatranes C₁₃H₈(R)Ge(OCH₂CH₂)₃N (1 - 3) (1: R = H; 2: R = Me₃Si; 3: R = Me₃Ge) were prepared by the reaction of 9-tribromogermyl derivatives of fluorene C₁₃H₈(R)GeBr₃ (4 - 6) with N(CH₂CH₂OSnAlk₃)₃ (7: Alk = Et; 8: Alk = Bu). 1-(9-Trimethylstannyl-9-fluorenyl)germatrane (14) was synthesised by the reaction of the germatrane (1) with Me₃SnNMe₂. Formulas and structures were established by elemental analyses, (₁H, ₁₃C) NMR spectroscopy and mass spectrometry; crystal structures of 2 and 14 are reported.

Full text of DOI:10.1515/znb-1998-1101

9
-Silyl(-Germyl,-Stannyl) Substituted Derivatives of l-(9-Fluorenyl)-
germatranes. Synthesis, Characterisation, and Crystal Structures
Galina S. Zaitseva3’*, Sergey S. Karlov3, Bettina A. Siggelkowb, Evgeni V. Avtomonovb,
Andrei V. Churakovc, Judith A. K. Howard0, Jörg Lorberthb’*
3
Chemistry Department, Moscow State University,
B-234 Vorob’evy Gory, 119899 Moscow, Russia
b Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Straße, D-35032 Marburg / Lahn, Germany
c Department of Chemistry, University of Durham, Science Laboratories,
South Road, Durham, DH 1 3LE, England
Z. Naturforsch. 53 b, 1247-1254 (1998); received June 15, 1998
Germanium, Germatrane, Organotin Reagents, X-Ray Data, NMR Data
9
-Trimethylsilyl- and 9-trimethylgermyl substituted derivatives of l-(9-fluorenyl)germ-
atranes C i3H8(R)Ge(OCH2CH2)3N (1 - 3) (1: R = H; 2: R = Me3Si; 3: R = Me3Ge)
were prepared by the reaction of 9-tribromogermyl derivatives of fluorene C i3H8(R)GeBr3
(
9
4 - 6) with N(CH2CH20SnAlk3)3 (7: Aik = Et; 8: Aik = Bu). l-(9-Trimethylstannyl-
-fluorenyl)germatrane (14) was synthesised by the reaction of the germatrane (1) with
Me3SnNMe2. Formulas and structures were established by elemental analyses, ('H, i3C) NMR
spectroscopy and mass spectrometry; crystal structures of 2 and 14 are reported.
Introduction
metallatranes. In the course of our investigations
1 2 ] we have focussed our efforts on the
synthesis, structural characterisation, and reactiv-
ity studies of (5-aza-2,8,9-trioxa-l-germabicyclo-
[
6 -
Metallatranes are a well-known and inten-
sively studied class of compounds compris-
ing a number of hypervalent Main Group Ele-
ments [1]. Metallatranes of the Group 14 elements
N(CH2CHRO)3MX (M = Si, Ge, Sn) received par-
ticular attention due to the question about the nature
of (N—>M)-transannular interaction [1 -3].
[
3.3.3]undecanes) with fluorenyl substituents in the
-position, including germatranes bearing an orga-
noelement group Me.^M (M = Si, Ge, Sn) in the
-position of the fluorenyl fragment. Some prelim-
1
9
inary work has recently been published [13]. A
combination of a germatrane moiety with the ster-
ically demanding, electronegative fluorenyl frag-
ment should allow us to study this combination with
respect to special properties of these molecules, par-
ticularly to the nature of the Ge<—N transannular
bond and, last but not least, for further functionali-
sation of germatranes.
Hypercoordination in the Group 14 metallatranes
leads to some unique chemical properties of the
compounds which render them significantly dif-
ferent from simply tetracoordinated derivatives of
these elements. In addition, interest in metallatranes
arises from their potential pharmacological activity
[3, 4]. Since germatranes are much less toxic then
isostructural silatranes, hence some examples have
already found practical application [5].
Results and Discussion
As yet, however, all reported examples of germa-
tranes are restricted to rather simple structures and
very little is known about functionally substituted
derivatives.
The main object of our studies is to function-
alise the relatively simple and readily available
Organotin compounds are common reagents in
organic synthesis [14]. Our recent synthetic studies
showed, that an “organotin route” for the forma-
tion of the "‘atrane"’ framework [10 - 13], e. g. the
reaction of organotrihalogermanes with organotin
derivatives of tris(2 -hydroxyalkyl)amines, is a gen-
eral pathway and allows syntheses of various ger-
matranes bearing a functional group, including
*
Reprint requests to Prof. Dr. J. Lorberth
or Dr. G. S. Zaitseva.
0
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248________ G. S. Zaitseva et al. • 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of l-(9-Fluorenyl)germ atranes
(25 - 30 h) than that for the 9-tribromogermyl-
fluorenes. However, this method allows a prepara-
tion of the corresponding germatranes in reasonable
yields (~ 60%). A synthesis of mixtures (A, B) was
carried out by treatment of 9-bromofluorenes 9 and
GeBrj
N(CH2CH2OSnAlk3)3
,8 ___________
7
-
3 AIk3SnBr
1
0 with GeCl2 dioxane which is more readily avail-
4
-6
able than the dibromo analogue (Scheme 3).
4
5
H
Et3Sn
1
2
H
M e3Si
M e3Si
Bu-iSn
6
M e3Ge
3
M e3Ge
Mixture A, R' = H
Mixture B, R’= M e3Si
9
,10
Scheme 1.
9
H
- 3 Bu3SnHaI
1
0
M e3Si
germatranes with Ge-C bonds which are sensitive
towards nucleophilic or electrophilic attack [1 1 , 1 2 ],
This method was used for the construction of
the “atrane” skeleton in our present work: Reac-
tions of the corresponding tribromogermylfluorenes
1
,2
Scheme 3.
9
-Bromo-9-trimethylsilylfluorene (10) and 9-
4
- 6 with tris(2-trialkylstannoxyethyl)amines 7, 8
bromo-9-trimethylgermylfluorene (11) can be pre-
pared starting from compounds 12 and 13, respec-
tively (Scheme 4).
under mild conditions afford germatranes 1-3 in
good to excellent yields (Scheme 1). These reac-
tions proceed smoothly after mixing of the reagents
in CHCI3, followed by stirring the reaction mixture
for 4 - 5 h at room temperature. After addition of
«
-hexane the resulting germatranes are precipitated
and separated by filtration. Analytically pure sam-
ples are obtained by washing the precipitates with
12,13
10,11
«
-hexane, recrystallisation from «-hexane, and fi-
12
13
Si
Ge
nally drying in vacuo. Trialkylbromostannanes are
formed as by-products of this transmetallation re-
action and can be recovered almost quantitatively.
The 9-tribromogermylfiuorenes 4 - 6 were ob-
tained by oxidative addition of the corresponding
Scheme 4.
The tin analogue l-(9-trimethylstannyl-9-fluor-
enyl)germatrane (14) can be synthesised from ger-
matrane 1 (Scheme 5) by reaction of the acidic hy-
drogen atom at the C(9) atom of the fluorene with a
strong base like trimethyltin dimethylamide.
9
-bromofluorenes 9 -11 to GeBr2 •dioxane in boil-
ing dioxane (Scheme 2).
Scheme 2.
Scheme 5.
Germatranes 1 and2 can also be successfully syn-
thesised by transesterification of a mixture of 9-tri-
The chemical potential of compounds 1 - 3 and
halogermylfluorenes (A, B) with ester 8. For this 14 as useful precursors for newly functionalised ger-
reaction completion needs a longer period of time matranes is based on the presence of an acidic C(9)
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G. S. Zaitseva et al. • 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of l-(9-Fluorenyl)germ atranes________ 1249
Table I. 'H and l3C NMR data for fluorenyl derivatives
- 6, 9 -14.
of peaks at m/z 130 has been attributed to the ion
GeN(CH2)3+, which is consistent with the germa-
trane structure. In the case of 14 the molecular ion
peak is only 6 % of the base peak. In the case of 2
and 3 the molecular ion peak is observed with an
intensity of 45%. Other intensities > 5% of the base
peak are quoted without assignment.
1
'
H [6, ppm]
I3C [6, ppm]
Comp.
Me3M
C(9)H
Me?M
C(9)
1
1
9
2
3
0.03
0.02
—
3.30
3.97
5.99
—
-2.68
-3.07
—
42.73
42.23
46.00
54.00
53.03
54.17
57.80
57.23
44.50
50.42
49.85
48.75
10
0.02
0.08
—
-3.35
-3.27
—
1
1
—
X-ray crystal structure determination of
N(CH2CH20 )3Ge(Me3Si)Cn HH(2) and
N(CH2CH20 )3Ge(Me3Sn)C,3H8 (14)
4
4.96
—
—
4.12
—
—
5
6
1
2
3
0.09
0.29
—
-0.23
-0.08
-0.16
-1.29
-1.21
—
-1.59
-1.81
-8.15
The crystal structures of germatranes 2 and 14
were determined by single crystal X-ray diffractom-
etry. Experimental data are summarised in Table II,
important atomic distances and bond angles in Ta-
bles III - VI. The molecular structures of the two
14
—
hydrogen atom, on a reactive metal-to-carbon bond
C-M (M = Si, Ge, Sn), and on the properties of the
aromatic ring system.
Synthesis and characterisation of compounds 1
and 4 were already described in a preliminary re-
port [13].
New compounds 2,3, 5,6, and 14 were charac-
terised by elemental analyses and ('H , 13C) NMR
spectroscopy. Compounds 2, 3, 5, 6, 11, 13, and 14
were also characterised by mass spectrometry.
The 'H and l3C NMR spectra are in accordance
with the suggested structures of the compounds: In
the 1H NMR spectra of 2, 3 and 14 the signals of
the methylene protons of the germatrane skeleton
appear as a set of two pseudo-triplets at 2 .6 6 - 2.71
(
isostructural) compounds are shown in Fig. 1 and
Fig. 2.
The coordination polyhedra of the germanium
atoms in 2 and 14 have the same structural features
common for germatrane derivatives [6 b, 11 - 13, 15-
2
0 ], /. e. a distorted trigonal bipyramidal coordina-
tion at germanium with N and C atoms in the apical
positions and three oxygen atoms in equatorial posi-
tions. The germanium atoms are displaced by 0.22
and 0.24 A, respectively, from the plane defined
by three oxygen atoms. The N-Ge-C fragments
in both molecules are almost linear (177.99(11)°
and 176.6(2)°). The N-Ge distances (2.202(3) and
2
.206(6) A) are in the normal range for germatranes
containing the N-Ge-C moiety (2.16 - 2.32 A) [11,
(
NCH2) and 3.6 - 3.71 (OCH2) ppm, a AA'XX' spin
1
1
3]. The Ge-Cfluorene bond lengths of 1.987(3) 2 and
.964(6) A 14 are somewhat smaller, but in the case
system (J = 5.5 -.5.8 Hz). This pattern is a general
feature of the “atrane” framework for a variety of
germatranes. In the l3C NMR spectra of 2, 3 and
of the silylated derivative this distance is almost
identical to that observed for a closely related ger-
matrane N[CH2CH20 ]3GeCi3H9 (1.991(3) A) [13],
Typical conformational disorder of the germa-
1
4 the signals of the carbon atoms of the “atrane”
skeleton appear at 52.1 - 52.8 (NCH2) and 57.0 -
7.3 (OCH?) ppm [1, 3, 6 - 13]. Chemical shifts of
5
the hydrogen and carbon atoms of the Me3M and trane cage has been observed for both 2 and 14 [11,
fluorenyl groups are found in the expected range; a 12]. All five-membered rings of the atrane skeleton
possess “envelope”-like conformation. The carbon
selection of NMR data is presented in Table I.
In the mass spectra of 2 and 3, the peak of high- atoms in the a-positions with respect to the nitrogen
est intensity corresponds to the germatranyl ion, re- atom form the “flaps” of these “envelopes” [2 1 ].
sulting from the loss of the apical substituent from
Interestingly, a second form of disorder has been
the parent ion. This behaviour is analogous to that found for the stannylated compound: The position
observed for 1-allylgermatrane [1 1 ] and for germa- of oxygen atom 0(3) is split into two different sites
trane 1 [13] and is assumed to reflect the relative in the equatorial plane of the trigonal bipyramid.
bond strength of the Ge-O ring bonds. In the case To the best of our knowledge, this type of disorder
of 14 the base peak corresponds to the ion result- is the first case for atrane molecules. The proxim-
ing from the loss of one methyl group. A cluster ity of the Me3Sn substituent to this oxygen atom
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250________ G. S. Zaitseva et al. • 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of l-(9-Fluorenyl)germ atranes
Table II. Crystal data, data collection, structure solution and refinement parameters for 2 and 14.
Empirical formula
Formula weight
Colour, habit
Crystal size [mm]
Crystal system
CnH29GeN03Sn
546.74
C22H29GeNOiSi
456.14
Colourless block
0.40 x 0.30 x 0.20
Orthorhombic
Pbcn, Z = 8
a = 14.6386(2)
b = 20.7826(2)
c — 14.6409(1)
4454.17(8)
Colourless nugget
0.16 x 0.13 x 0.12
Orthorhombic
Pbcn, Z = 8
a= 14.538(3)
b = 20.622(4)
c = 14.637(3)
4388.2(15)
1.381
Space group
Unit cell dimensions [A]
Volume [A3]
Density (calculated) [g cm -3 ]
Absorption coefficient [mm-
F(000)
1.631
2.493
2192
1.473
1904
Diffractometer
Siemens SMART
100.0(2)
Stoe-IPDS
190(2)
Temperature [K]
Radiation (A [A])
Scan mode
— graphite monochromatised M oKa (0.71073) —
omega
phi
(
9-Range [deg]
1.70 to 24.99
2.21 to 25.90
Index ranges
-1 3 < h < 18 ,-2 6 < k < 26,
1 8 < l< 19
-17 < h < 17, -2 2 < k < 25,
-1 7 < / < 17
-
Reflections collected
Independent reflections
Data reduction
25508
3923 [R(int) = 0.0557]
24304
4247 [fl(int) = 0.0825]
Siemens SAINT (Siemens Analytical Stoe-INTEGRATE
X-ray Instruments, 1995)
Absorption correction
Min. and max. transmission
Solution method
Multi-scan (SHELXTL, 1994) [29]
0.26 and 0.38
Direct methods (SHELX-86) [30]
none
0.80 and 0.84
Direct methods (SHELXS-97) [32]
Refinement method
Program
— Full-matrix least-squares on F2 —
SHELXL-93 [31 ]
SHELXL-97 [33]
Hydrogen atoms treatment
Data / parameters
Goodness-of-fit on F2
R \, wR2, [I > 2 cr(I)]
R \, wi?2 (all data)
All H atoms were placed in calculated positions and refined using a riding model
3845 / 288
1.314
4247 / 284
0.934
0.0454,0.1015
0.0547, 0.1078
0.00046(6)
1.67
0.0394,0.0829
0.0680, 0.0905
none
Extinction coefficient
Largest diff. peak
0.46
—3i
hole [e / A
-0.84
-0.51
(
C(14)-0(3b) (2.90 A) may be a plausible explana-
spectra (EI-MS) were recorded on a Varian CH-7a in-
strument using electron impact with an ionisation energy
of 70 eV; all assignments were made with respect to the
most abundant isotopes.
tion for this phenomenon.
Experimental
Solutions of Az-butyllitium in n-hexane were obtained
from Aldrich Chemical Company and were analysed by
the Gilman double titration method prior to use [22],
Tris(2-trialkylstannoxyalkyl)amines (7, 8) were pre-
pared according to a modified procedure using an excess
of trialkylmethoxystannanes [11 - 13, 23],
9-Trimethylsilylfluorene (12) and 9-trimethylgermyl-
fluorene (13) were synthesised by the reaction of fluo-
renyllithium with Me.^SiCl or Me.^GeBr, respectively.
All solvents were dried by standard methods and dis-
tilled prior to use; melting points are uncorrected. Ele-
mental analyses were carried out by the Microanalytical
Laboratory of the Chemistry Department of the Moscow
State University and of the Fachbereich Chemie of the
Philipps-University Marburg (Heraeus-Rapid-Analyser).
NMR spectra were recorded at 25 °C on Varian VXR-
4
00 and Bruker AC 300 spectrometers, CDCL was used
as a solvent and for internal deuterium lock. The chemical
shifts (6) of the 'H and l3C NMR resonances are given
in ppm relative to internal TMS. Assignments of the l3C
NMR data were supported by APT experiments. Mass
9
-Trimethylsilylfluorene (12) [24]
'H NMR (CDCI ): 6 = 0.03 (s, 9H, SiM e3); 3.30 (s,
1H, SiCH); 7.75 - 7.70, 7.63 - 7.58, 7.39 - 7.30 (3 m.
3
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G. S. Zaitseva et al. • 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of 1-(9-Fluorenyl)germatranes
1251
Table III. Selected bond lengths (A) for 2.
Ge-N
2.202(3)
1.793(2)
1.784(4)
1.785(2)
1.441(11)
1.427(8)
1.581(9)
1.506(14)
1.602(8)
1.425(9)
1.922(3)
Ge-C(l)
1.987(3)
1.389(4)
1.399(5)
1.412(4)
1.445(9)
1.561(6)
1.429(7)
1.467(11)
1.470(7)
1.610(9)
0.22b
Ge-O(l)
Ge-0(2)
Ge-0(3)
N-C(18)
N-C(20)
N-C(22)
C(17)-C(18)
C(19)-C(20)
C(21)-C(22)
Si-C(l)
0(1)-C(17)
0(3)-C(21)
0(2)-C(19)
N-C(18A)
N-C(20A)
N-C(22A)
C(17)-C(18A)
C(19)-C(20A)
C(21)-C(22A)
Ge-PLa
a PL means an equatorial plane defined by 0(1), 0(2), 0(3)
atoms;bpositive sign indicates that Ge atom is displaced towards
carbon atom C( 1).
Table IV. Selected bond angles (deg) for 2.
0
0
0
0
0
(2)-Ge-0(3)
(2)-Ge-0(l)
(l)-Ge-0(3)
( 1)-Ge-N
119.02(14) 0(1)-Ge-C(l)
117.53(12) 0(2)-Ge-C(l)
118.22(14) 0(3)-Ge-C(l)
82.10(10) 0(3)-Ge-N
97.46(12)
96.54(12)
100.3(2)
81.98(12)
177.99(11)
Fig. 1. Molecular structure of 2.
6 = -3.35 (SiMe3); 54.00 (SiCBr); 120.05 (C-4,5); 125.54,
(2)-Ge-N
82.99(10) C(l)-Ge-N
C(18)-N-C(20)
C(18)-N-C(22)
C(20)-N-C(22)
C(18)-N-Ge
C(20)-N-Ge
C(22)-N-Ge
120.1(6)
111.5(6)
109.4(5)
105.9(5)
105.5(3)
102.8(4)
C(18A)-N-C(20A) 109.7(5)
C(18A)-N-C(22A) 117.8(5)
C(20A)-N-C(22A) 112.8(5)
C(18A)-N-Ge
C(20A)-N-Ge
C(22A)-N-Ge
1
1
27.25, 127.62 (C -l,8 ; C-2,7; C-3,6 ); 139.07 (C-l 1,12).
47.43 (C -l0,13).
105.4(4)
102.2(3)
107.7(3)
9
-Bromo-9-trimethylgermylfluorene (11)
0
0
0
(1)-C(17)-C(18) 113.6(5)
(2)-C(19)-C(20) 111.6(4)
(3)-C(21)-C(22) 114.9(4)
0(1)-C(17)-C(18A) 115.2(4)
0(2)-C( 19)-C(20A) 112.8(3)
0(3)-C(21)-C(22A) 112.0(4)
M.p. 135 - 137 °C. 'H NMR (CDC13): 6 = 0.08 (s,
9
H, GeMe3); 7.76 - 7.69, 7.62 - 7.56, 7.38 - 7.29 (3 m,
Ar, 8H). 13C NMR (CDC13): 6 = -3.27 (GeMe3); 53.03
(GeCBr); 119.93 (C-4,5); 124.77, 127.36, 127.25 (C -l,8 ;
C-2,7; C-3,6 ); 138.23 (C-l 1,12); 147.97 (C -10,13). EI-
MS, m/z (rel. int., assign.): 360 (8%, M+), 268 (4%,
M+-CH3-Br), 253 (4%, M+-2CH3-Br), 243 (7%, M+-Br-
GeMe3); 237 (3%, M+-3CH3-Br), 166 (17%, C I3H ,0),
165 (49%, C L3 H9), 164 (26%, C 13H8), 163 (30%, C I3H7),
119 (100%, GeMe3).
GeX2 dioxanes were synthesized as described in the
literature [27].
Tribromogermyl derivatives 4 - 6 were obtained by re-
fluxing a mixture of GeBr2 dioxane and the corresponding
N-C(18)-C(17)
N-C(20)-C(19)
N-C(22)-C(21)
C(17)-0(1)-Ge
C(19)-0(2)-Ge
108.7(8)
105.2(5)
106.1(6)
120.0(2)
119.5(2)
N-C(18A)-C(17)
N-C(20A)-C(19)
N-(22A)-C(21)
C(21)-0(3)-Ge
110.6(6)
105.2(4)
104.4(5)
120.8(2)
Ar, 8 H). I3C NMR (CDCI3): 6 = -2.68 (SiMe3), 42.73
SiCH), 119.87 (C-4,5), 123.97, 125.93, 125.17 (C -l,8 ;
C-2,7; C-3,6 ), 140.38 (C-l 1,12), 145.64 (C-10,13).
(
9
-Trimethylgermylfluorene (13) [25]
1
H NMR (CDCI3): 6 =0.02 (s, 9H,GeMe3); 3.97 (s, 1H,
GeCH); 7.88 - 7.85,7.49 - 7.47,7.36 - 7.27 (3 m, Ar, 8 H).
3C NMR (CDCI3): 6 = -3.07 (GeMe3), 42.23 (GeCH),
19.83 (C-4,5), 123.36, 124.99, 125.96 (C -l,8 ; C-2,7;
C-3,6 ), 139.79 (C-l 1,12), 146.17 (C -10,13). EI-MS, m/z
9
-bromofIuorene (9 -11). 9-Tribromogermyl-fluorene (4)
was prepared according to the literature [13].
,
1
9
-Tribromogermyl-9-trimethylgermylfluorene (6)
mixture of 11 (1.00 g, 2.76 mmol) and
(rel. int., assign.): 284 (10%, M+), 166 (8 %, C |3H I0), 165
A
(
57%, C 13H9), 163 (7%, C i3H7), 119 (100%, GeMe3).
G eB^dioxane 0.9 g (2.81 mmol) in 6 ml dioxane was
heated to reflux for 8 h; solvent was removed in vacuo.
Chloroform (2 ml) and «-hexane (3 ml) were added to
the residual red oil and the mixture was stored for 12 h at
9
-Bromofluorenes (10,11) were synthesized by the re-
action of the corresponding fluorenes (12,13) with NBS.
9
-Bromo-9-trimethylsilylfluorene (10) [26]
H NMR (CDC13): 6 = 0.02 (s, 9H, SiMe3); 1.1A-7.71,
.6 3 -7 .5 9 ,7 .7 4 -7 .7 1 (3 m, Ar, 8 H). I3C NMR (CDC13):
-
18 °C. A precipitate was filtered off and dried in vacuo.
1
After recrystallisation («-hexane / CHC13) 0.61 g (37%)
of the product was recoverd, m. p. 119 - 121°C.
7
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1
252________ G. S. Zaitseva et al. ■9-Silyl(-Germyl,-StannyI) Substituted Derivatives of l-(9-Fluorenyl)germ atranes
Table V. Selected bond lengths (A) for 14.
Ge-C(9)
Ge-0(2)
Ge-0( 1)
N-C(17)
N-C(19)
N-C(21)
1.964(6)
1.790(4)
1.797(5)
1.39(2)
1.603(12)
1.481(12)
1.388(8)
1.417(7)
1.56(2)
Ge-N
2.206(6)
1.811(11)
1.846(10)
1.50(2)
1.356(14)
1.588(14)
1.351(12)
1.544(14)
1.42(2)
Ge-0(3B)
Ge-0(3A)
N-C(170)
N-C( 190)
N-C(210)
0(3A)-C(22)
0(3B)-C(22)
C( 18)-C( 170)
C(20)-C(190)
C(22)-C(210)
Ge-PLa
0
0
(1)-C(18)
(2)-C(20)
C(18)-C(17)
C(20)-C( 19)
C(22)-C(21)
Sn-C(9)
1.463(13)
1.68(2)
2.212(6)
1.64(2)
1.48(2)
0.24b
a PL means an equatorial plane defined by four oxygen atoms
(1), 0(2), 0(3A) and 0(3B); positive sign indicates that Ge
0
atom is displaced towards carbon atom C(9).
Table VI. Selected bond angles (deg) for 14.
0
0
0
0
0
0
0
(2)-Ge-0(l)
(2)-Ge-0(3B)
(1 )-Ge-0(3B)
(2)-Ge-0(3A)
( 1)-Ge-0(3A)
(2)-Ge-N
119.4(2) 0(2)-Ge-C(9)
130.8(4) 0(1)-Ge-C(9)
106.2(4) 0(3B)-Ge-C(9)
107.3(4) 0(3A)-Ge-C(9)
126.7(4) C(9)-Ge-N
100.3(2)
96.0(2)
92.2(4)
99.7(4)
176.6(2)
86.0(4)
Fig. 2. Molecular structure of 14.
'
H NMR (CDC13): 6 = 0.09 (s, 9H, SiM e3); 7.99 -
.95, 7.55 - 7.52, 7.47 - 7.43 (3 m, Ar, 8 H). I3C NMR
CDCfO: Ö= -1.29 (SiMe3); 57.80 (GeCSi); 120.40 (C-
,5); 125.44,127.51,127.03 (C -1,8 ;C-2,7; C-3,6); 140.66
7
83.0(2) 0(3B)-Ge-N
81.8(2) 0(3A)-Ge-N
(
( 1)-Ge-N
79.6(3)
4
C(17)-N-C(21)
C(17)-N-C(19)
C(19)-N-C(21)
C(17)-N-Ge
C(19)-N-Ge
C(21)-N-Ge
118.4(9) C( 170)-N-C(210)
110.6(9) C(170)-N-C(190)
106.7(7) C(190)-N-C(210)
108.7(7) C(170)-N-Ge
103.6(5) C(190)-N-Ge
107.9(6) C(210)-N-Ge
120.6(4) C(22)-0(3A)-Ge
120.0(4) C(22)-0(3B)-Ge
106.6(10)
122.7(10)
114.6(8)
103.7(8)
105.9(7)
100.4(6)
120.0(7)
111.7(7)
(C-l 1,12); 141.28 (C-10,13). EI-MS, m/z (rel. int., as-
sign.): 550 (8%, M+), 396 (69%, M+-SiM e3-Br), 243
(
52%, C ,3H8Br), 237 (31%, C 13H8SiMe3), 222 (43%,
C ,3H8SiMe2); 180 (5%, C 13H9Me), 179 (23%), 178
26%), 165 (22%, Ci3H9), 164 (10%, C13H8), 163 (12%,
(
C(18)-0(1)-Ge
C(20)-0(2)-Ge
C 13H7), 73 (100%, SiMe3).
0
0
0
(1)-C(18)-C(17) 113.9(7) 0(1)-C(18)-C(170) 115.0(9)
(2)-C(20)-C(19) 115.4(7) 0(2)-C(20)-C( 190) 109.1(7)
(3A)-C(22)-C(21) 104.4(7) 0(3B)-C(22)-C(210) 105.4(8)
Analysis for Ci6Hi7Br3GeSi (549.70)
Calcd C 34.96 H3.12% ,
Found C 34.83 H 3.36%.
N-C(17)-C(18)
N-C(19)-C(20)
N-C(21)-C(22)
108.8(10) N-C(170)-C(18)
104.6(8) N-C(190)-C(20)
100.4(8) N-C(210)-C(22)
110.7(11)
107.8(9)
104.6(8)
Mixture B(CuHx(SiMe
3
)GeBrnCl -n) was obtained ac-
3
cording to the same procedure as for 6 , starting from 9-
bromo-9-trimethylsilylfluorene (10) with GeCh-dioxane.
'
H NMR (CDC1):<5 = 0.29 (s, 9H, GeMe3); 7.95-7.93,
’
H NMR(CDC13): 6 = 0.09, 0.11, 0.13, 0.14 (4s, 9H,
7
.53 - 7.49, 7.45 - 7.42 (3 m, Ar, H). I3C NMR
8
SiMe3); 7.95 - 7.85, 7.61 - 7.47, 7.45 - 7.30 (3m, 8H, Ar)
Mixture A (C/jHgGeBrnCLi-n) was obtained by an anal-
ogous reaction.
(
(
CDCI3): 8 = -1.21 (GeMe3); 57.23 (GeCGe); 120.32
C-4,5); 124.84, 127.28, 127.01 (C-1,8; C-2,7; C-3,6);
1
40.70 (C -11,12); 141.40 (C-10,13). EI-MS, m/z (rel.
int., assign.): 594 (2%, M+), 396 (19%, M+-Br-GeMe3),
Synthesis ofgermatranes 1-3
2
2
68 (9%, M+-GeBr3-CH3), 253 (9%, M+-GeBr3-2CH3),
43(36% ,C ,3H8Br), 180 (22%, C ,3H9CH3), 179(100% ,
1
- 3 were obtained according to published procedures
by reacting esters 7, 8 with 9-tribromogermylfluorenes (4
6 ) [11, 12], 1 was prepared by the reaction of 7 with 4,
C 13H8CH3), 178 (40%, C i3H8CH2), 165 (77%, C i3H9),
64 (17%, C 13H8), 163 (22%, C |3H7), 119 (70%, GeMe3).
-
1
as described in [13], and also by the reaction of ester 8
with mixture A (Ci3H9GeBr„Cl3_„).
Analysis for Ci6H |7Br3Ge2 (594.20)
Calcd C 32.34 H 2.88%,
/
-(9-Trimethylsilyl-9-fluorenyl)germatrane (2)
Found C 32.05 FI 2.51%.
9
-Tribromogermyl-9-trimethylsilylfluorene (5) was ob-
A mixture of 0.09 g (0.16 mmol) of 9-tribromogermyl-
tained according to the procedure for 6, and recrystallised
9-trimethylsilylfluorene (5), 0.24 g (0.24 mmol) of tris(2-
from «-hexane. Yield 69%, m. p. 121 - 124 °C.
tributylstannoxyethyl)amine (8 ) and 6 ml of chloroform
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G. S. Zaitseva e t al. • 9-Silyl(-G erm yl,-Stannyl) Substituted Derivatives o f 1-(9-Fluorenyl)germatranes_________1253
was stirred at room temperature for 4 h. After removal of
the solvent, addition of 4 ml n-hexane gave a white solid
which was filtered off and washed with n-hexane (5x5
ml). Recrystallisation from «-hexane / chloroform (3:1)
yielded 0.07 g (95 %), m. p. 212 - 214 °C.
1-(9-Trimethylstannyl-9-fluorenyl)germatrane (14)
A
mixture of 0.54
g
(1.3 mmol) of l-(9-
(3.85 mmol) of
fluorenyl)germatrane (1) and 0.8
g
Me3SnNMe2 was heated to reflux in THF (6 ml) for 10
h. After cooling to room temperature and with addition
of 3 ml of /7-hexane, colourless crystals grew at -1 8 °C,
which were dried in a vacuum; yield 0.59 g (77%), m. p.
'
H NMR (CDCI3): 6 = -0.23 (s, 9H, SiMe3); 3.62(t,
6
H, OCH2); 2.66 (t, 6 H, NCH2); 7.92 - 7.87, 7.84 - 7.80,
.26 - 7.20(3m, 8H, Ar); l3C NMR (CDCI3): 8 = -1.59
7
1
9 5-1 9 6 °C.
H NMR (CDCI3): 6 = -0.16 (s, 9H, SnMe3); 3.71
(
SiMe3), 50.42 (SiCGe), 52.77 (NCH2), 57.30 (OCH2),
19.24 (C-4,5), 123.91, 125.22, 125.67 (C -l,8 ; C-2,7;
C-3,6 ), 139.97 (C-l 1,12), 147.45 (C-10,13). EI-MS, m/z
rel. int., assign.): 457 (45%, M+), 237 (6 %, C ,3H8SiM e3),
'
1
(t, 6 H, OCH2); 2.71 (t, 6 H, NCH2); 7.97 - 7.8, 7.32
- 7.23 (2m, 8H, Ar); ,3C NMR (CDCI3): 6 = -8.15
(SnMe3), 48.75 (GeCSn), 52.09 (NCH2), 56.98 (OCH2),
(
2
20 (100%, A = N(CH2CH20 ) 3Ge), 165 (14%, C I3H9),
1
19.19 (C-4,5), 122.76, 124.19, 125.09 (C -l,8; C-2,7;
C-3,6), 138.03 (C-l 1,12), 148.51 (C-10,13). EI-MS, m/z
rel. int., assign.): 547 (6%, M+), 532 (100%, M+-CH3),
1
60 (9%, A-2CH20 ), 146 (44%, A-CH20-C H 2CH20 ),
7
3 (22%, SiMe3).
(
Analysis for C22H29GeN0 3 Si (456.15)
Calcd C 57.93 H6.41 N 3.07%,
Found C 57.26 H 6.42 N3.10% .
502 (4%, M+-3CH3), 283 (5%, C i3H8Sn), 220 (39%,
A = N(CH2CH20 ) 3Ge), 165 (32%, C 13H9), 160 (9%, A-
2CH20 ), 146 (9%, A-CH20-C H 2CH20 ).
Germatrane 2 was also prepared by the reaction of ester
with mixture B (Ci3H8(SiMe3)GeBr„Cl3_„).
Analysis for C22H29GeN0 3 Sn (540.75)
Calcd C 48.33 H 5.35 N 2.56%,
Found C 48.70 H 5.24 N 2.35%.
8
l-(9-Trimethylgermyl-9-fluorenyl)germatrane (3)
X-ray crystal structure determination [28]
Table II [29 - 33] summarises crystal data as well as de-
tails of data collection and structure refinement for com-
pounds 2 and 14. All non-hydrogen atoms of 2 and -
except for C(14) - of 14 were refined anisotropically; the
hydrogen atoms were placed on calculated positions and
refined using a riding model.
This synthesis was carried out as described for 2, start-
ing from 6 and 8 ; yield 85%, m.p. 184 - 186~°C.
'
H NMR (CDCI3): 6 = -0.08 (s, 9H, GeMe3); 3.67(t,
6
H, OCH2); 2.70 (t, 6 H, NCH2); 7.92 - 7.90, 7.87 - 7.84,
.27 - 7.25(3m, 8H, Ar); l3C NMR (CDCI3): <5 = -1.81
7
(
1
GeMe3), 49.85 (GeCGe), 52.56 (NCH2), 57.16 (OCH2),
19.16 (C-4,5), 123.67, 125.07, 125.24 (C -l,8 ; C-2,7;
C-3,6 ), 139.35 (C-l 1,12), 148.10 (C-10,13). EI-MS, tn/z
rel. int., assign.): 501 (45%, M+), 486 (33%, M+-CH3),
66 (30%), 220 (100%, A = N(CH2CH20 ) 3Ge), 179
Acknowledgements
A research grant for G. S. Z. and for E. V. A. within the
framework the “HSP-III Programm der Hessischen Lan-
desregierung” and support from the Fonds der Deutschen
Chemischen Industrie VCI for J. L., as well as from the
Russian Foundation for Basic Research under Grant No
98-03-32988a for S. S. K., are gratefully acknowledged.
A. V. C thanks The Royal Society and the University of
Durham for financial support.
(
2
(
(
69%), 165 (78%, C 13H9), 160 (29%, A-2CH20 ), 146
70%, A-CH20-C H 2CH20 ), 119 (37%, GeMe3).
Analysis for C22H29Ge2N0 3 (500.66)
Calcd C 52.78 H 5.84 N 2.80%,
Found C 52.38 H 5.48 N 2.65%.
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1
254________ G. S. Zaitseva et al. • 9-Silyl(-Germyl,-Stannyl) Substituted Derivatives of l-(9-Fluorenyl)germ atranes
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