Synthesis and characterization of 3- and 4-phenylgermatranes: X-ray crystal structures of N(CH2CH2O) 2(CH2CHPhO)GeZ (Z=F, OSiMe3, C≡CPh) and N(CH2CH2O)2 (CHPhCH2O)GeOH

Article abstract of DOI:10.1016/S0022-328X(03)00225-0

Reaction of excess of product A [(HOCH₂CH₂)₂NCH₂ CH(Ph)OH (1):(HOCH₂CH₂)₂NCH(Ph) CH₂OH (2)=9:1] with GeCl₄ led to a mixture of 1-chloro-3-phenylgermatrane (3) and 1-chloro-4-phenylgermatrane (4). Compound 4 was isolated in yield 9% from this mixture. Reaction of (EtO)₃GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane (5) was prepared in yield 31% by treatment of (EtO)₃GeC≡CPh with product A. Reaction of product A with mixture of GeO₂ and H₂O produced N(CH₂CH₂O)₂ (CH₂CHPhO)GeOH (6) in yield 73%. The presence of N(CH₂CH₂O)₂(CHPhCH₂O)GeOH (7) among the products of this reaction was confirmed by ¹H-, ¹³C-NMR spectroscopy and X-ray analysis. N(CH₂CH₂O)₂(CH₂CHPhO)GeF (8) is formed by the treatment of 6 with BF₃·Et₂O. N(CH₂CH₂O)₂(CH₂CHPhO) GeOSiMe₃ (9) was obtained by silylation of 6 with (Me₃Si)₂NH or Me₃SiCl-Et₃N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded [N(CH₂CH₂O)₂(CH₂CHPhO)Ge] ₂O (10). 9 reacted with SOCl₂, Me₃SiBr and Me₃SiOTf to give N(CH₂CH₂O)₂(CH₂CHPhO)GeX (3, X=Cl; 11, X=Br; 12, X=OTf), respectively. Reaction of 11 with Et₃SnOMe led to the formation of N(CH₂CH₂O)₂(CH₂CHPhO)GeOMe (13). Germatranes N(CH₂CH₂O)₂ (CH₂CHPhO)GeY [14, Y=Flu (fluorenyl); 15, Y=N(SiMe₃)₂] were obtained from the nucleophilic substitution of the substituent X in N(CH₂CH₂O) ₂(CH₂CHPhO)GeX (X=OSiMe₃, Br) with the corresponding LiY. All compounds were characterized by ¹H- and ¹³C-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5 and 7-9 were determined by X-ray diffraction studies.

Full text of DOI:10.1016/S0022-328X(03)00225-0

Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
www.elsevier.com/locate/jorganchem
Synthesis and characterization of 3- and 4-phenylgermatranes: X-ray
crystal structures of N(CH2CH2O)2(CH2CHPhO)GeZ (ZꢀF,
OSiMe3, CꢀCPh) and N(CH2CH2O)2(CHPhCH2O)GeOH
/
/
Ekaterina V. Gauchenova a, Sergey S. Karlov a,*, Anastasia A. Selina a, Eleonora
S. Chernyshova a, Andrei V. Churakov b, Judith A.K. Howard c, Nikolaj A. Troitsky d,
Stanislav N. Tandura d, Jorg Lorberth e,*, Galina S. Zaitseva a
¨
a Chemistry Department, Moscow State University, Leninskie Gory, Moscow 119899, Russia
b Institute of General and Inorganic Chemistry, RAS, Leninskii Pr. 31, Moscow 119991, Russia
c Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, UK
d Institute of Organic Chemistry, RAS, Leninskii Pr. 47, Moscow 119991, Russia
e Fachbereich Chemie, Philipps-Universitat Marburg, Hans-Meerwein-Strasse, D-35032 Marburg/Lahn, Germany
¨
Received 28 October 2002; received in revised form 15 January 2003; accepted 10 March 2003
Abstract
Reaction of excess of product A [(HOCH2CH2)2NCH2CH(Ph)OH (1):(HOCH2CH2)2NCH(Ph)CH2OH (2)ꢀ9:1] with GeCl4 led
/
to a mixture of 1-chloro-3-phenylgermatrane (3) and 1-chloro-4-phenylgermatrane (4). Compound 4 was isolated in yield 9% from
this mixture. Reaction of (EtO)3GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane (5) was prepared
in yield 31% by treatment of (EtO)3GeCꢀ/CPh with product A. Reaction of product A with mixture of GeO2 and H2O produced
N(CH2CH2O)2(CH2CHPhO)GeOH (6) in yield 73%. The presence of N(CH2CH2O)2(CHPhCH2O)GeOH (7) among the products
of this reaction was confirmed by 1H-, 13C-NMR spectroscopy and X-ray analysis. N(CH2CH2O)2(CH2CHPhO)GeF (8) is formed
by the treatment of 6 with BF3×
or Me3SiClꢁEt3N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded
[N(CH2CH2O)2(CH2CHPhO)Ge]2O (10). 9 reacted with SOCl2, Me3SiBr and Me3SiOTf to give N(CH2CH2O)2(CH2CHPhO)GeX
(3, XꢀCl; 11, XꢀBr; 12, XꢀOTf), respectively. Reaction of 11 with Et3SnOMe led to the formation of N(CH2CH2O)2(CH2CH-
PhO)GeOMe (13). Germatranes N(CH2CH2O)2(CH2CHPhO)GeY [14, YꢀFlu (fluorenyl); 15, YꢀN(SiMe3)2] were obtained from
the nucleophilic substitution of the substituent X in N(CH2CH2O)2(CH2CHPhO)GeX (XꢀOSiMe3, Br) with the corresponding
LiY. All compounds were characterized by H- and 13C-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5
and 7ꢁ9 were determined by X-ray diffraction studies.
/Et2O. N(CH2CH2O)2(CH2CHPhO)GeOSiMe3 (9) was obtained by silylation of 6 with (Me3Si)2NH
/
/
/
/
/
/
/
1
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Germatrane; NMR spectroscopy; Crystal structures
1. Introduction
being the subject of interest. The chemistry of metalla-
tranes with different substituents in atrane moiety has
been studied to a very limited extent. Among them
3,7,10-trimethyl-substituted germatranes are the most
known [1]. There are only few reports concerning
germatranes bearing other groups attached to carbon
atoms of atrane fragment. At the same time, one could
expect that the presence of phenyl group at 3- or 4-
position of atrane skeleton can considerably influence
The chemistry of metal derivatives of aminoalcohols
such as trialkanolamine*
considerable attention mostly from the theoretical point
of view, the nature of intramolecular N0M interaction
/
metallatranes*has attracted
/
/
* Corresponding authors. Tel./fax: ꢂ
E-mail addresses: sergej@org.chem.msu.su (S.S. Karlov),
lorberth@chemie.uni-marburg.de (J. Lorberth).
/
49-6421-282-5642.
the nature of the N0
/
Ge bond and affect the reactivity,
structure and physical properties of these molecules.
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00225-0

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
9
In our opinion, successful synthesis of 3- and 4-
phenyl-substituted derivatives will provide an opportu-
nity to prepare more complex molecules by functiona-
lization owing to not only apical group at the
germanium atom but also substituents in atrane moiety.
Among 3-phenyl-substituted germatranes, only 1-
hydroxy, 1-methyl and 1-phenyl derivatives have been
reported in the literature when we began this study. The
syntheses of these compounds as well as IR data have
ð2Þ
It should be noted that only one germatrane contain-
ing a substituent in the position 4 of the atrane fragment
been described [2ꢁ4]. Mass spectra of 1,3-diphenylger-
/
matrane were also studied [2]. However, no NMR
spectroscopy and X-ray diffraction have been reported
so far. To the best of our knowledge, no 4-phenylger-
matranes have been investigated prior to our study.
In this context, we describe synthesis and character-
ization of a series of functionally substituted 3- and 4-
phenylgermatranes and crystal structures determination
has previously been reported*1-hydroxy-4-ethylgerma-
trane; its structure was determined by X-ray diffraction
studies [6].
Compound 3 was obtained in moderate yield in the
case of the interaction of triethoxychlorogermane with
product A (Eq. (3)).
/
(EtO)3GeCl product A
0
3
(3)
of 5 and 7ꢁ9.
/
ꢃ3EtOH
The transesterification of (triethoxygermyl)phenyla-
cetylene with trialkanolamines (1:2ꢀ9:1) led to 1-
(phenylethynyl)-3-phenylgermatrane (5) in yield 31%
/
2. Results and discussion
(Eq. (4)).
2.1. Starting 2-[bis(2-hydroxyethyl)amino]-1-phenyl-1-
ethanol (1) and 2-[bis(2-hydroxyethyl)amino]-2-phenyl-
1-ethanol (2)
ð4Þ
For the synthesis of C-phenyl-substituted trialkano-
lamines 1 and 2, we examined reaction of diethanola-
mine with styrene oxide [5]. A mixture of reagents was
maintained at reflux for 4 h. In actuality, the ring
opening reaction imposes the formation of two isomers,
1
and in fact, H- and 13C-NMR spectroscopy shows the
reaction product (product A) to contain a mixture of
isomeric aminoalcohols 1 and 2 in a ca. 9:1 ratio (Eq.
(1)).
2.3. 3- and 4-Phenyl-substituted 1-hydroxygermatranes:
preparation and use for synthesis of new germatranes
Recently, there was reported an efficient approach for
the synthesis of various functionally substituted germa-
tranes starting from the most simple and available
ð1Þ
germatranes*/1-hydroxygermatranes [7]. Reaction of
GeO2 with product A (1:2ꢀ/9:1) in the presence of
water was studied for the preparation of phenyl-
substituted 1-hydroxygermatranes. Previously this reac-
tion has been described [8]. However, composition of the
product obtained in yield 89% was confirmed only by
elemental analysis data. We have found that a solid
precipitates after boiling of reagents mixture up to
complete dissolution of GeO2 and cooling of reaction
mixture. Filtration of this precipitate followed by
washing with ethanol and drying in vacuo at 1 Torr
yielded analytically pure sample of 1-hydroxy-3-phenyl-
2.2. Synthesis of 3- and 4-phenyl-substituted germatranes
by reaction of product A with GeCl4, (EtO)3GeCl and
(EtO)3GeCꢀ/CPh
Reaction of excess of product A with GeCl4 gave a
mixture of 1-chloro-3-phenylgermatrane (3) and 1-
chloro-4-phenylgermatrane (4). After a number of
manipulations (see Section 3), germatrane 4 was ob-
tained as an analytically pure sample in yield 9% (Eq.
(2)). However, we were unable to obtain the major
isomer 3 as an individual product in this reaction.
1
germatrane (6). H- and 13C-NMR and EI-MS studies
confirm its structure. From filtrate additional amount of

10
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
1
solid was isolated. According to the H- and 13C-NMR
spectroscopy and mass spectrometry, this substance
contained isomeric 1-hydroxy-4-phenylgermatrane (7)
and compound 10 (see below) besides germatrane 6 (Eq.
(5)). Crystals of compound 7 suitable for X-ray struc-
tural analysis could be found.
Si)2NH dissolution of solid takes place; after cooling of
the reaction mixture formation of the precipitate
N(CH2CHRO)3GeOSiMe3 (yieldsꢀ90%) was ob-
/
served. In the case of 6, boiling of reaction mixture for
several hours have not led to the dissolution of solid.
After filtration of hot reaction mixture and cooling of
(5)
1-Hydroxygermatrane 6 was used for the preparation
of 1-fluoro-3-phenylgermatrane (8) and 1-trimethylsi-
loxy-3-phenylgermatrane (9).
filtrate, compound 9 was obtained in yield 16% (Eq.
(7a)). In our opinion low yield of 9 can be accounted for
easiness of formation in conditions of reaction (7a)
N(CH2CHPhO)3GeOGe(OCHPhCH2)3N (10) which is
inert with respect to (Me3Si)2NH. Taking it into
account, we have carried out the silylation of hydro-
The reaction of germatrane 6 with BF3×
/
Et2O pro-
ceeded in mild conditions and led to compound 8 with
high yield (Eq. (6)).
(6)
Previously silylation by means of (Me3Si)2NH was
xygermatrane 6 in milder conditions. The treatment of a
studied for N(CH2CHRO)3GeOH (Rꢀ/H, Me) [9,10]. It
suspension of germatrane 6 in CHCl3 with Me3SiClꢁ
/
was shown that in the course of boiling of a suspension
of 1-hydroxygermatrane in xylene with excess of (Me3-
Et3N at room temperature gave 1-trimethylsiloxy-3-
phenylgermatrane (9) in yield 65% (Eq. (7b)).
(7)

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
11
Actually, the formation of germatrane 10 was ob-
served at refluxing of a suspension of 6 in xylene with
simultaneous removing of water formed by azeotropic
distillation (Eq. (8)).
Halogenides and triflates of tetracoordinated germa-
nium are reactive reagents for metallation and widely
used as the key reagents for the synthesis of various
functionally substituted organogermanium compounds
(8)
Previously we have shown that N(CH2CHRO)3GeX
[12,13]. In contrast to above, corresponding derivatives
of germatranes were studied in this context to the
considerably less extent. For example, their reactions
with organometallic compounds have been studied only
recently [11].
Reaction of 1-bromogermatrane 11 with Et3SnOMe
led to 1-methoxy-3-phenylgermatrane (13) in practically
quantitative yield (Eq. (10)).
(Rꢀ
/
H, Me; XꢀCl, Br, OTf) can be obtained smoothly
/
and in high yields on the basis of corresponding 1-
trimethylsiloxygermatranes [10,11]. We have studied the
behaviour of 1-trimethylsiloxy-3-phenylgermatrane (9)
in analogous reactions (Eq. (9)). N(CH2CHRO)3GeO-
SiMe3 (Rꢀ/H, Me) easily reacts with thionyl chloride
(4ꢁ8 h, room temperature) with the formation of
/
appropriate 1-chlorogermatranes [11]. On the contrary,
interaction of germatrane 9 with SOCl2 proceeds more
slowly (24 h) and gives 1-chloro-3-phenylgermatrane (3)
in yield 49%. Boiling of a suspension of germatrane 9 in
xylene with Me3SiBr led to 1-bromo-3-phenylgerma-
trane (11) in yield 85%. Reaction of Me3SiOTf with
germatrane 9 at room temperature gives germatranyltri-
flate (12) in quantitative yield (Eq. (9)).
ð10Þ
It should be noted that the attempted synthesis of 1-
ethoxy-3-phenylgermatrane by reaction of (EtO)4Ge
with product A (1:2ꢀ9:1) failed.
/
Surprisingly, but in germatrane chemistry the ap-
proach to functionalized germatranes by the reaction of
simple and available germatranes with lithium reagents
has not been used before work of our group [7].
Probably, hopelessness of the research like that has
been assigned to the assumption about destruction of
atrane moiety in the course of these transformations.
Indeed, these reactions may proceed through intermedi-
ates I and II and in the case of strong nucleophilic
reagents (n-BuLi) unselective process of cleavage of Geꢁ
/
(9)
O bonds leads to destruction of atrane fragment. In the
case of weaker nucleophiles, the proceeding of the
reaction via intermediate I is more favorable and results

12
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
Table 1
Selected 1H-NMR spectral data for 4 and 9 a
Proton
Chemical shift, d (ppm)
4 (4-Ph) c
Couple
Coupling constant, J (Hz) b
9 (3-Ph) d
4 (4-Ph)
9 (3-Ph)
Ha3
4.26
3.87
4.19
4.80
H3a H4a
H3a H4e
H3e H4a
H3e H4e
H7a H6a
H7a H6e
H7e H6a
H7e H6e
H1a0 H1a1
H1a0 H1e1
H1e0 H1a1
H1e0 H1e1
10.7
10.8
4.1
He3
ꢁ/
ꢁ/
5.0
Ha4
2.43
3.06
3.75
3.93
2.96
2.97
3.71
3.89
2.77
2.83
ꢁ/
ꢁ/
He4
ꢁ/
ꢁ/
Ha7
3.68
3.80
3.26
2.21
4.07
3.90
2.82
3.10
11.0
5.7
5.7
3.8
11.4
4.3
6.3
3.7
11.3
3.8
3.4
7.4
11.2
5.9
3.7
6.0
He7
Ha6
He6
H1a0
H1e0
H1a1
H1e1
a
500.132 MHz, 298 K. Abbreviations: see figure for the labeling scheme.
b
c
Geminal coupling constants for OCH2 and NCH2 protons equal ꢀ
/
11.1 and ꢀ
/
12.5 Hz, respectively.
In DMSO-d6.
In CDCl3.
d
in 1-substituted germatranes.
ð11Þ
We tested germatranes 9 and 11 in the reactions with
fluorenyllithium and LiN(SiMe3)2. Corresponding ger-
X
Y
matranes 14 and 15 were obtained in yields 60ꢁ70% (Eq.
(11)).
/
9
11
OsiMe3
Br
14
15
Flu
N(SiMe3)2
The new compounds 3ꢁ15 were characterized by
/
Table 2
Selected 13C-NMR Spectral Data for 4 and 9 a
elemental analyses, IR (5), H-, 13C-NMR spectroscopy
and mass spectrometry.
1
Carbon
d (ppm)
4 b
9 c
2.4. NMR spectra
C3
60.10
57.24
68.57
56.92
C7
1H- and 13C-NMR spectra are in accord with the
suggested structures. The proton spectra of 3ꢁ15 are
C10
C4
57.46
61.13
56.85
59.02
/
C6
47.42
46.13
52.93
52.37
evidently complicated by the asymmetric carbon atoms
C4 or C3. The signals of the protons of the germatrane
skeleton appear as complex multiplets: two AA?XX?
spin systems for N(CH2CH2O)2 and one ABX for
NCHCH2O or NCH2CHO.
C11
Ph
131.67 (Ci)
129.72 (Co)
129.41 (Cp)
128.66 (Cm)
141.48 (CI)
128.50 (Co)
127.76 (Cp)
125.43 (Cm)
1
The H and 13C data for 4 and 9 are collected in
a
125.77 MHz, 298 K. Abbreviations: see figure for the labeling
Tables 1 and 2, respectively. The assignments of the
1
signals have been made on the basis of 2D H NOESY,
scheme.
b
In DMSO-d6.
In CDCl3, d 13C(SiMe3) 2.25 ppm.
1
1
2D H COSY, and 2D H, 13C correlations.
c

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
13
Table 3
Selected bond lengths (A) and angles (8) for 5
Table 1) were observed. Thus compounds 4 and 9
possess the rigid structure.
˚
1
It should be noted that H-NMR spectra of germa-
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
C(1)ꢁ
N(1)ꢁ
N(1)ꢁ
N(1)ꢁ
/
O(3)
O(1)
O(2)
C(1)
N(1)
1.775(4) O(1)ꢁ
1.787(3) O(2)ꢁ
1.789(4) O(3)ꢁ
1.914(7) C(2)ꢁ
2.166(6) C(9)ꢁ
1.192(9) C(10)ꢁ
1.451(8) C(11)ꢁ
1.481(7) C(13)ꢁ
1.484(7)
/
C(12)
C(13)
C(14)
1.400(7)
1.423(5)
1.423(6)
1.445(7)
1.504(7)
1.527(6)
1.503(8)
1.504(6)
tranes N(CH2CH2O)3GeX contain two triplets due to
the fast conversion on the NMR time scale of their five-
membered rings. Vicinal coupling constants are aver-
/
/
/
/
/
/
C(3)
/
/
C(14)
aged (J :8 Hz) because of an exchange process between
/
/
C(2)
/
C(13)
C(12)
C(15)
two states where each proton occupies alternately
equatorial and axial positions [15].
/
C(9)
/
/
C(10)
C(11)
/
/
The values of proton chemical shifts in germatranes 4
and 9 confirm a rigid structure, too. Two rings
Ge(OCH2CH2)2N with frozen conformation in 9 have
average values of proton chemical shifts (OCH2: 3.82
ppm and NCH2: 2.88 ppm) which are close to the values
(3.84 and 2.85 ppm, respectively) for chemically equiva-
lent protons in model germatrane N(CH2CH2O)3GeO-
SiMe3 with fast interconversion [17]. Thus, the Ph group
in position 3 of atrane skeleton does not affect shielding
of other rings protons, i.e. it is placed on maximum long
distances from unsubstituted rings (in the equatorial
place).
For germatrane 4, the average values of chemical
shifts in non-substituted rings 3.86 ppm (OCH2)2 and
3.06 ppm (only three NCH protons) are close to 3.97
and 2.98 ppm for 1-chlorogermatrane [17]. However, the
rest of NCH proton has abnormal great shielding (d(H6e)
2.21 ppm) caused by its close contact to Ph group.
Thus the NMR spectroscopy data show that com-
pound 9 maintains in solution the primary geometry
found in the solid state. The structure of 4 in solution is
similar to that found for closely related germatrane 7 in
the solid state.
O(3)ꢁ
O(3)ꢁ
O(1)ꢁ
O(3)ꢁ
O(1)ꢁ
O(2)ꢁ
O(3)ꢁ
O(1)ꢁ
O(2)ꢁ
C(1)ꢁ
C(2)ꢁ
C(9)ꢁ
C(9)ꢁ
C(10)ꢁ
C(9)ꢁN(1)ꢁ
/
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
Ge(1)ꢁ
C(1)ꢁ
N(1)ꢁ
N(1)ꢁ
/
O(1)
O(2)
O(2)
C(1)
C(1)
C(1)
N(1)
N(1)
N(1)
N(1)
116.8(2) C(10)ꢁ
118.6(2) C(11)ꢁ
120.7(2) C(12)ꢁ
98.6(3) C(13)ꢁ
94.5(2) C(14)ꢁ
96.9(2) C(1)ꢁC(2)ꢁ
83.7(2) N(1)ꢁC(9)ꢁ
82.6(2) N(1)ꢁC(10)ꢁ
83.7(2) N(1)ꢁC(11)ꢁ
176.9(2) O(1)ꢁC(12)ꢁ
169.3(6) O(2)ꢁC(13)ꢁ
114.7(4) O(2)ꢁC(13)ꢁ
114.2(5) C(15)ꢁC(13)ꢁ
112.2(5) O(3)ꢁC(14)ꢁC(9)
104.8(4)
/
N(1)ꢁ
N(1)ꢁ
O(1)ꢁ
O(2)ꢁ
O(3)ꢁ
/
Ge(1)
Ge(1)
Ge(1)
Ge(1)
Ge(1)
105.0(3)
104.7(3)
120.1(3)
118.6(3)
117.0(3)
176.8(5)
107.6(4)
108.4(4)
107.8(5)
109.9(4)
109.9(3)
109.0(4)
110.4(4)
109.9(4)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
C(3)
/
/
/
/
C(14)
/
/
/
/C(13)
/
/
/
/C(12)
/
/
/
/
C(11)
C(15)
C(10)
/
/
Ge(1)
/
/
/
/
C(10)
/
/
/
/
C(11)
/
/
C(10)
/
N(1)ꢁ
/
C(11)
/
/
/
/
Ge(1)
In 1H-NMR spectrum of 1-chloro-4-phenylgerma-
Table 4
trane (4), the proton H4a have two various protonꢁ
/
˚
Selected bond lengths (A) and angles (8) for 7
proton coupling constants 10.7 Hz (with axial H3a) and
5.2 Hz (H3e). The similar values of constants (10.9 and
5.9 Hz) were observed for closely related silatranes
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
/
O(4)
O(1)
O(3)
O(2)
N
1.767(2)
1.773(2)
1.781(2)
1.805(2)
2.187(2)
1.471(3)
1.479(4)
1.482(3)
1.413(4)
C(11)ꢁ
/
C(12)
1.498(5)
1.414(3)
2.19(4)
/
O(2)ꢁ
O(2)ꢁ
/
C(22)
H(1)#1
/
/
/
C(21)ꢁ
C(21)ꢁ
O(3)ꢁ
C(31)ꢁ
O(4)ꢁH(1)
/
C(22)
1.498(4)
1.514(4)
1.403(4)
1.487(5)
0.71(4)
N(CHMeCH2O)3SiX (XꢀOMe, Ph) [14].
/
/
/
C(1)
For 1-trimethylsiloxy-3-phenylgermatrane (9) protons
H3a have likewise vicinal coupling constants 10.8 (with
axial H4a proton) and 4.1 Hz (H4e). For other germa-
tranes with the same structure, the constants are
Nꢁ
Nꢁ
Nꢁ
/
C(11)
C(31)
C(21)
/
C(32)
C(32)
/
/
/
/
O(1)ꢁ
O(4)ꢁ
O(4)ꢁ
O(1)ꢁ
O(3)ꢁ
O(4)ꢁ
O(1)ꢁ
O(3)ꢁ
O(2)ꢁ
C(11)ꢁ
C(11)ꢁ
C(31)ꢁ
C(11)ꢁ
C(31)ꢁ
/
C(12)
similar*
MeO)GeH] [15] and 10.4 and 4.3 Hz [N(CH2CH2O)2-
(CH2CHRO)GeH, RꢀOCH2Ph] [16]. Two consider-
ably different vicinal protonꢁproton coupling constants
/
11.1 and 3.7 Hz [N(CH2CH2O)2(CH2CH-
/
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Nꢁ
Nꢁ
Nꢁ
Nꢁ
Nꢁ
/
O(1)
O(3)
O(3)
O(2)
N
96.4(1)
C(21)ꢁ
C(12)ꢁ
NꢁC(11)ꢁ
C(22)ꢁO(2)ꢁ
GeꢁO(2)ꢁH(1)#1
C(21)ꢁ
C(21)ꢁ
82.88(9) C(22)ꢁ
/
Nꢁ
O(1)ꢁ
C(12)
H(1)#1
/Ge
104.0(2)
117.5(2)
108.3(2)
/
/
97.6(1)
/
/
Ge
/
/
117.5(1)
120.7(1)
178.4(1)
/
/
/
/
/
/
/
100(1)
/
/
/
/
/
134.5(9)
106.9(2)
116.0(2)
114.9(2)
110.4(2)
118.3(2)
108.6(3)
111.9(3)
at the exo-substituted carbon atom in germatranes 4
and 9 should be explained by the fact that this fragment
exists in a single frozen conformation. The proton
adjusted to C3 atom is located axial and, hence, Ph
group occupies the equatorial position. For non-sub-
stituted rings N(CH2CH2O)2 in 4 and 9 similar values of
/
/N
84.11(9) Nꢁ
/
/C(22)
/
/N
83.54(9) Nꢁ
/
/C(1)
/
/N
/
C(21)ꢁ
/C(1)
/
/
C(31)
C(21)
C(21)
Ge
113.6(3)
116.7(2)
112.8(2)
103.8(2)
104.1(2)
O(2)ꢁ
C(32)ꢁ
NꢁC(31)ꢁ
O(3)ꢁC(32)ꢁ
GeꢁO(4)ꢁH(1)
/
C(22)ꢁ
/
C(21)
/
/
/
O(3)ꢁ
/
Ge
/
/
/
/C(32)
/
/
/
/
C(31)
two vicinal coupling constants for axialꢁ
/axial and
/
/
Ge
/
/
107(3)
axialꢁequatorial protons (11.0ꢁ11.4 and 3.4ꢁ
/
/
/6.3 Hz,

14
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
Table 5
˚
Selected bond lengths (A) and angles (8) for 8
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
O(1)ꢁ
O(2)ꢁ
O(3)ꢁ
/
F(1)
O(3)
O(2)
O(1)
N(1)
1.749(2)
1.765(2)
1.766(2)
1.774(2)
2.108(2)
1.432(4)
1.426(4)
1.421(4)
N(1)ꢁ
N(1)ꢁ
N(1)ꢁ
C(1)ꢁ
C(1)ꢁ
C(3)ꢁ
C(5)ꢁ
/
C(3)
C(2)
C(6)
1.477(4)
1.480(3)
1.486(4)
1.516(4)
1.523(4)
1.516(4)
1.503(5)
/
/
/
/
/
/
C(7)
C(2)
C(4)
C(6)
/
/
/
C(1)
C(5)
C(4)
/
/
/
/
F(1)ꢁ
F(1)ꢁ
O(3)ꢁ
F(1)ꢁGeꢁ
O(3)ꢁGeꢁ
O(2)ꢁGeꢁ
F(1)ꢁGeꢁ
O(3)ꢁGeꢁ
O(2)ꢁGeꢁ
O(1)ꢁGeꢁ
C(1)ꢁ
C(5)ꢁ
C(4)ꢁ
C(3)ꢁ
/
Geꢁ
Geꢁ
Geꢁ
/
O(3)
93.9(1)
94.1(1)
C(3)ꢁ
C(2)ꢁ
C(3)ꢁ
C(2)ꢁ
C(6)ꢁ
O(1)ꢁ
O(1)ꢁ
C(7)ꢁ
N(1)ꢁ
N(1)ꢁ
O(3)ꢁ
O(2)ꢁ
N(1)ꢁ
/
N(1)ꢁ
N(1)ꢁ
N(1)ꢁ
N(1)ꢁ
N(1)ꢁ
C(1)ꢁ
C(1)ꢁ
C(1)ꢁ
C(2)ꢁ
C(3)ꢁ
C(4)ꢁ
C(5)ꢁ
C(6)ꢁ
/
C(6)
C(6)
Ge
114.2(3)
112.8(2)
104.4(2)
105.3(2)
104.7(2)
109.2(2)
109.3(2)
110.7(2)
108.5(2)
107.3(3)
109.8(3)
111.0(3)
107.7(3)
/
/O(2)
/
/
/
/
O(2)
117.4(1)
93.81(9)
121.4(1)
119.9(1)
179.4(1)
85.99(9)
86.5(1)
/
/
/
/O(1)
/
/Ge
/
/
O(1)
O(1)
/
/Ge
/
/
/
/
C(7)
C(2)
/
/N(1)
/
/
Fig. 1. Molecular structure of 5. Hydrogen atoms are omitted for
clarity.
/
/
N(1)
N(1)
N(1)
/
/C(2)
/
/
/
/C(1)
/
/
85.73(9)
116.9(2)
115.0(2)
115.9(2)
114.1(2)
/
/C(4)
/
O(1)ꢁ
O(2)ꢁ
O(3)ꢁ
N(1)ꢁ
/
Ge
Ge
Ge
/
/
C(3)
C(6)
/
/
/
/
/
/
/
/C(5)
/
/C(2)
2.5. Mass spectra
We have found major fragmentation pathways of 3-
phenyl-substituted germatranes under EI conditions.
The received data testify to two opportunities of
fragmentation of these molecules. The first way is
connected to dissociative ionization of Geꢁ
/X bond
Table 6
Selected bond lengths (A) and angles (8) for 9
˚
Fig. 2. Molecular structure of 8. Hydrogen atoms are omitted for
clarity.
Geꢁ
Geꢁ
Geꢁ
Geꢁ
/
O(1)
O(3)
O(2)
N
1.776(3)
1.789(2)
1.793(3)
2.170(4)
1.631(3)
1.861(4)
1.882(5)
1.325(7)
1.455(5)
1.678(7)
1.486(5)
O(3)ꢁ
C(21)ꢁ
C(32)ꢁ
C(32)ꢁ
C(22)ꢁ
C(11)ꢁ
C(11)ꢁ
C(16)ꢁ
C(15)ꢁ
C(14)ꢁ
C(12)ꢁ
/
C(32)
1.412(4)
1.508(7)
1.286(8)
1.619(8)
1.492(7)
1.36(1)
1.43(1)
1.38(1)
1.41(2)
1.39(2)
1.39(1)
/
/
C(22)
C(31A)
C(31B)
C(11)
C(16)
C(13)
C(15)
C(14)
C(12)
C(13)
with formation of germatranyl cation at m/e 296.
Further subsequent fragmentation proceeds through
consecutive elimination of PhCHO (m/e 190) and then
of CH2O (m/e 160) or group (OCH2CH2) (m/e 146) or
2CH2O (m/e 130). A cluster of peaks at m/e 130 has
been attributed to the ion GeN(CH2)3ꢂ, which is
consistent with the germatrane structure. This way is
/
/
/
/
Siꢁ
Siꢁ
Siꢁ
Nꢁ
Nꢁ
Nꢁ
/
O(1)
/
/
C(1)
/
/C(2)
/
/
C(31B)
C(21)
C(31A)
/
/
/
/
/
O(2)ꢁ
O(1)ꢁ
O(3)ꢁ
O(1)ꢁ
O(3)ꢁ
O(1)ꢁ
O(3)ꢁ
O(2)ꢁ
SiꢁO(1)ꢁ
C(21)ꢁNꢁ
C(21)ꢁNꢁ
C(31A)ꢁ
C(22)ꢁO(2)ꢁ
C(32)ꢁO(3)ꢁ
NꢁC(21)ꢁ
/C(22)
/
realized for germatranes containing labile Geꢁ
/X bond
/
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
Geꢁ
/
O(3)
O(3)#1
O(2)
O(2)
N
/
C(32)ꢁ
/
O(3)
120.1(5)
107.6(5)
108.0(4)
105.8(4)
115.8(4)
118.5(7)
123.1(7)
118.4(6)
122(1)
as compound 14 where the peak of highest intensity
corresponds to the germatranyl ion. This behaviour is
analogous to that observed for 1-(9-fluorenyl)germa-
/
/
116.5(2)
/
/N
/
/
/
C(11)
/
/
/
C(21)
/
/
/
C(21)
C(13)
C(22)
C(22)
C(15)
C(14)
C(12)
C(14)
C(11)
tranes [7,18ꢁ
weakness of the Geꢁ
X fragment were found in mass spectrum of 14.
The second way is observed in 3-phenyl-substituted
germatranes with strong XꢁGeꢁN interaction. The first
step of fragmentation is elimination of PhCHO. For
compounds 5, 6, 8 and 9ꢁ13, the intensities of this peak
are 30ꢁ100%. There are intensive peaks of ions resulting
from the further loss of CH2O (13ꢁ94%). On the
/20] and assumed to reflect the relative
/
/
N
/
/
C bond. No ions contained NꢁGeꢁ
/
/
/
/
N
/
/
/
Ge
/
/
/
C(31A)
/
/
/
Ge
/
121(2)
/
/
/
Nꢁ
/Ge
/
118(2)
120(1)
/
/Ge
/
/
/
/Ge
/
120.4(8)
/
/
/
C(22)
/

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
15
However, in the case of 15 the base peak corresponds
to the ion resulting from the loss of one Me group.
Analogously, the same ion [Mꢂꢃ
Me] was detected for
compound 9 (49%).
/
It should be noted that the fragmentation pathway of
compound 4 containing phenyl substituent in position 4
of atrane skeleton is different from that found for 3-
phenyl-substituted analogue 3. Thus, the first step of
fragmentation is elimination of CH2O. The intensity of
this peak is 63%. The intensity of the peak correspond-
ing to the ion resulting from the loss of another CH2O
group is 28%. Of interest, the peaks corresponding to
ions [Mꢂꢃ
/
CH2Oꢃ
/
Ph] and [Mꢂꢃ
/
2CH2OꢃPh] are
/
sufficiently intensive, too. Analogously, for compound
3 intensity of germatranyl cation peak (m/e 296) was
found to be 11%.
For all studied compounds, the molecular ion peak is
not observed or its intensity is smaller than 1% of the ion
current, except compound 8 (8%).
2.6. Crystal structures
Fig. 3. Molecular structure of 7. Two symmetry-related molecules
forming dimer are shown. Hydrogen atoms (except H(1)) are omitted
for clarity.
To the best of our knowledge, compounds 5 and 7ꢁ9
are the first structurally characterized germatrane deri-
vatives with Ph substituent in atrane skeleton. Selected
/
bond lengths and angles for 5 and 7ꢁ
/9 are listed in
contrary, intensities of germatranyl cation peak (m/e
296) for these compounds are smaller than 12%.
Tables 3ꢁ6, respectively.
/
The molecular structures of 5 and 8 are shown in Figs.
1 and 2. The main geometrical parameters of 5 and 8 are
close to those previously reported for N(CH2CH2O)3-
GeCꢀ/CPh [21] and N(CH2CH2O)3GeF [22], respec-
tively. The coordination polyhedron of the germanium
atom in both compounds represents a distorted trigonal
bipyramid with N(1) and C(1) (for compound 5) or F(1)
(for compound 8) atoms in the axial positions and the
three oxygen atoms occupying equatorial sites. The
˚
Nax distance in 5 (2.166(6) A) lies within
value of Geꢁ
/
˚
the typical range for germatranes (2.081(5)ꢁ2.32(1) A)
/
[23,24] and clearly verifies the existence of Geꢁ
/
N
transannular bond in 5. The germanium atom in
˚
compound 5 is displaced by 0.21 A (DGe) towards the
phenylethynyl substituent from the equatorial plane
defined by three oxygen atoms.
˚
Nax distance in 8 (2.108(2) A) is
The value of Geꢁ
/
noticeably shorter than that in 5. This is in accordance
with the general trend observed in atrane structures:
more electronegative groups X yield shorter Mꢁ
/
N
transannular distances. It should be noted that DGe
(0.12 A) is smaller than that in compound 5. Thus, the
˚
coordination polyhedron of the germanium atom in
compound 8 is closer to an ideal trigonal bipyramid
than in 5.
The molecular structure of 7 is shown in Fig. 3. The
main geometrical parameters of 7 are very close to those
previously reported for N(CH2CH2O)2(CHEtCH2O)-
Fig. 4. Molecular structure of 9. Hydrogen atoms are omitted for
clarity.
GeOH [6] and N(CH2CH2O)3GeOH×
/
H2O [25]. Thus,

16
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
the presence of alkyl or aryl groups in position 4 of
atrane skeleton does not influence on coordination
matranes studied by X-ray analysis demonstrate the
same structural trends as unsubstituted derivatives.
polyhedron of germanium atom. It should be noted
˚
O(4)ax distance (1.767(2) A) is
that the value of Geꢁ
Oeq distances
(1.773(2), 1.781(2), 1.805(2) A). In crystal two molecules
/
3. Experimental
noticeably smaller than the values of Geꢁ
/
˚
3.1. General comments
of 7 form centrosymmetric dimers by H-bonding (O(2)ꢁ
/
˚
O(4A) distance is 2.90 A).
The synthesis of 3ꢁ
/
5 and 8ꢁ15 were carried out under
/
The molecular structure of 9 is shown in Fig. 4. In
contrast to above, the key geometrical parameters of 9
are different to those previously reported for closely
argon atmosphere and standard Schlenk techniques. All
solvents were dried by standard methods and distilled
before use. Solutions of n-butyllithium in hexane were
commercially obtained and analyzed regularly by the
Gilman double titration method [28]. NMR spectra
were recorded at 25 8C in CDCl3 and DMSO-d6 with
internal deuterium lock, on Varian VXR 400, Bruker
DRX 500, Bruker AC 300 spectrometers. Chemical
shifts in the 1H- and 13C-NMR spectra are given in
ppm relative to internal TMS; in 19F-NMR experiments
CFCl3 was used as an external standard. Elemental
analyses were carried out by the Microanalytical La-
boratory of the Chemistry Department of the Moscow
State University. Mass spectra (EI-MS, 70 eV) were
recorded on a VARIAN CH-7a device; all assignments
were made with reference to the most abundant
isotopes.
related N(CH2CH2O)3GeOSiMe3 [26]. The value of
˚
N transannular distance (2.170(4) A) is noticeably
Geꢁ
/
longer than the values of Geꢁ
/
N distances in N(CH2-
˚
CH2O)3GeOSiMe3 (2.128(5) A). On the contrary, Geꢁ
/
˚
Oax bond in 9 (1.776(3) A) is shorter than that in 1-
˚
trimethylsiloxygermatrane (1.810(5) A). Other main
geometrical parameters of 9 and N(CH2CH2O)3GeO-
SiMe3 are very close with the exception of Siꢁ
/
Oꢁ
/
Ge
angle. The value of this angle in compound 9 (140.6(2)8)
is larger than that in N(CH2CH2O)3GeOSiMe3
(133.0(4)8) as well as in N(CH2CH2O)3GeOSiMe2(2-
thienyl) (134.8(3)8), N(CH2CH2O)3GeOꢁ
/
SiMe(2-thie-
nyl)2 (139.6(3)8) [26] and N(CH2CH2O)3GeOSiMe2Vin
(136.5(4)8) [27].
According to X-ray data phenyl substituent (com-
pounds 5 and 7ꢁ9) lies in equatorial position with
/
3.2. Reaction of diethanolamine with 2-phenyloxirane:
synthesis of product A
[(HOCH2CH2)2NCH2CH(Ph)OH (1):(HOCH2-
respect to corresponding five-membered rings (solid
state). The same results were found for the solution
from NMR data (see above).
CH2)2NCH(Ph)CH2OH (2)ꢀ9:1]
/
In conclusion, synthetic approaches to 3-phenyl-
substituted germatranes were investigated and the
structure and the chemical behaviour of these com-
pounds were studied. In general, no significant differ-
ence, which could appear due to the steric effect of the
phenyl group, was detected in reactivity of 3-phenyl-
substituted germatranes and their unsubstituted or
3,7,10-trimethyl-substituted analogues. However, we
note the increased easiness of germanoxane 10 forma-
tion from 1-hydroxygermatrane 6 in comparison with
unsubstituted 1-hydroxygermatrane. Complete analysis
of the 1H and 13C spectra of 3- and 4-phenyl-substituted
germatranes has been performed. All protons and
carbons of atrane skeleton (substituted and unsubsti-
tuted rings) were found non-equivalent. The structure of
3-phenyl- and 4-phenyl-substituted germatranes in solu-
tion (NMR data) strongly differs from the structure of
unsubstituted germatranes. The latter undergoes the
intramolecular conformation conversions while the in-
troduction of phenyl group in atrane framework leads to
‘‘freezing’’ of these processes. This ‘‘frozen’’ conforma-
tion is the same in solution and in solid state (X-ray
data). It should be noted that the structure of germa-
trane 9 in solid state is notably different from that of
unsubstituted analogue. Other phenyl-substituted ger-
A mixture of (HOCH2CH2)2NH (19.03 g, 0.181 mol)
and 2-phenyloxirane (21.08 g, 0.181 mol) was refluxed
for 4 h. The distillation gave 35 g (85%) of product A as
a mixture of 1 (90%) and 2 (10%); b.p. 205ꢁ
/
207 8C per 1
1
Torr [5]: 218ꢁ
/
222 8C per 3 Torr. H-NMR (CDCl3): d
5.14 (broad s, 3H, OH); 7.22, 7.30 (2m, aromatic
protons); multiplets of (AA?XX?)2 and ABX systems
of NCH2CH2O, NCH2CHO and NCHCH2O groups
protons*for 1: 2.46, 2.81, 3.53, 3.72, 4.76; for 2: 2.35,
/
2.64, 3.49, 3.61, 3.93, 4.03. 13C-NMR (CDCl3): 125.86,
127.42, 128.27, 141.89 (aromatic C for 1); 127.59,
128.20, 128.49, 136.31 (aromatic C for 2); 57.25, 59.40,
64.05, 70.98 [N(CH2CH2OH)2(CH2ꢁ
/
CHOH) in 1];
51.74, 59.18, 61.35, 64.62 [N(CH2CH2OH)2(CH-
CH2OH) in 2].
3.3. Reaction of GeCl4 with product A
Product A (4.46 g, 20 mmol) was added dropwise to a
solution of GeCl4 (1.06 g, 4.94 mmol) in 20 ml of THF.
Immediately formation of the salts [(1:2ꢀ
/
9:1)×/HCl] was
observed. The precipitate was filtered off and washed
with CH3CN. After removal of all volatiles from
combined filtrates in vacuo, the residue was dried in

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
17
vacuo and dissolved in 50 ml of boiling CH3CN. The
solution was cooled; the precipitate was filtered off and
benzene. The reaction mixture was stirred for 24 h at r.t.
A white solid was filtered off, washed with hexane (5ꢄ
10 ml), dried in vacuo and recrystallized from CHCl3ꢁ
hexane to give 1.57 g (31%) of 5. IR (thin film): n 2172
C). 1H-NMR (CDCl3): d 2.52, 2.83, 3.00,
/
recrystallized from CH2Cl2ꢁ
/
hexane. Yield of N(CH2-
CH2O)2(CHPhCH2O)GeCl (4): 0.15 g (9%). 1H- and
13C-NMR spectra (DMSO-d6) (Tables 1 and 2). EI-MS
/
cmꢃ1 (Cꢀ
/
m/e (rel. int.): [Mꢂ] 331 (0.2); [Mꢂꢃ
/
CH2O] 301 (63);
2CH2O] 271 (28); [Mꢂ
Cl] 266 (12); [Mꢂꢃ
CH2OꢃPh] 224 (45);
2CH2OꢃPh] 194 (39); [N(CH2)(CHC6H5)-
(CH2CH2O)] 162 (73); [N(CH2)(CHC6H5)] 118 (40);
[Mꢂꢃ
3CH2OꢃN(CH2)2(CHC6H5)] 109 (52); [C7H7]
91 (100); [HN(CH)(CH2)ꢃ(CH2CH2O)] 86 (92). Anal.
3.06, 3.79, 3.95, 4.83 (H-3) [7 m, (AA?XX?)2 and ABX
systems of NCH2CH2O and NCH2CHPhO groups
[Mꢂꢃ
CH2Oꢃ
[Mꢂꢃ
/
Cl] 296 (11); [Mꢂꢃ
/
ꢃ
/
/
/
/
protons], 7.07ꢁ
NMR (CDCl3): atrane C*
58.26, 68.53 (C-3); 90.91 (GeCꢀ
matic C*122.91, 125.73, 127.78, 127.90, 128.21, 128.49,
132.39, 141.13. EI-MS m/e (rel. int.): [Mꢂ] 397 (0.3);
[MꢂꢃC6H5CHO] 291 (48); [Mꢂꢃ
C6H5CHOꢃCH2O]
261 (13); [Mꢂꢃ
C6H5CHOꢃ2CH2OꢃN(CH2)3] 175
(31); [Mꢂꢃ
C6H5CHOꢃC6H5CꢀCꢃCH2CH2O] 146
/
7.50 (m, 10H, aromatic protons). 13C-
/
/
/51.69, 52.31, 56.8, 56.7,
/
); 99.29 (ꢀCPh); aro-
/
/
/
/
/
Found: C, 43.79; H, 4.80; Ge, 21.61. Calc. for
C12H16ClGeNO3 (330.22): C, 43.63; H, 4.88; Ge,
21.98%.
/
/
/
/
/
/
/
/
/
/
CH3CN was removed in vacuo from filtrate after
(100); [N(CH2)2CH2CH2O] 86 (14). Anal. Found: C,
60.92; H, 5.17; N, 3.28. Calc. for C20H21GeNO3 (396.0):
C, 60.66; H, 5.35; N, 3.54%.
1
separation of 4, the residue was dried in vacuo. In H-
NMR (CDCl3) spectra the signals of protons of
N(CH2CH2O)2(CH2CHPhO)GeCl (3) (mainly), [(1:2ꢀ
/
9:1)×HCl] and 4 were founded.
/
3.6. Reaction of GeO2ꢁH2O with product A: synthesis of
1-hydroxy-3-phenyl-germatrane,
N(CH2CH2O)2(CH2CHPhO)GeOH (6)
/
3.4. Synthesis of 1-chloro-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeCl (3)
A mixture of product A (18.69 g, 83 mmol), GeO2
(8.72 g, 83 mmol) and H2O (25 ml) was heated at reflux.
GeO2 has dissolved within 1 h. A precipitate was filtered
3.4.1. From reaction of (EtO)3GeCl with product A
Product A (1.48 g, 6.57 mmol) was added dropwise to
a solution of (EtO)3GeCl (1.6 g, 6.58 mmol) in 20 ml of
benzene. Immediate formation of the precipitate was
observed. The reaction mixture was stirred for 24 h, the
white solid was filtered off, washed with hexane and
dried in vacuo to give 1.19 g (55%) of 3. 1H-NMR
(CDCl3): d 2.64, 2.94, 3.12, 3.21, 3.89, 4.06, 4.95 (H-3) [7
m, (AA?XX?)2 and ABX systems of NCH2CH2O and
off, washed with EtOH (4ꢄ10 ml) and dried in vacuo;
/
19 g (73%) of 6 was obtained. 1H-NMR (CDCl3): d 1.62
(s, 1H, OH); 2.55, 2.89, 3.05, 3.13, 3.81, 3.97, 4.85 (H-3)
[7 m, (AA?XX?)2 and ABX systems of NCH2CH2O and
NCH2CHO groups protons]; 7.30ꢁ
matic protons). 13C-NMR (CDCl3): atrane C*
52.94, 56.81, 56.93, 58.87, 68.66 (C-3); aromatic C*
125.63, 128.05, 128.60, 140.83. EI-MS m/e (rel. int.):
[Mꢂ] 313 (0.2); [MꢂꢃC6H5CHO] 207 (77); [Mꢂꢃ
C6H5CHOꢃ C6H5CHOꢃCH2-
CH2O] 177 (61); [Mꢂꢃ
CH2Oꢃ C6H5-
OH] 146 (7); 134 (24); [Mꢂꢃ
CHOꢃ2CH2OꢃN(CH2)3] 91 (39); [N(CH2)2CH2-
/7.39 (m, 5H, aro-
/52.38,
/
NCH2CHPhO groups protons], 7.28ꢁ
aromatic protons). 13C-NMR (CDCl3): atrane C*
52.43, 52.98, 57.85, 57.98, 58.79, 69.75 (C-3); aromatic
C*122.91, 125.73, 127.78, 127.90, 128.21, 128.49,
132.39, 141.13. EI-MS m/e (rel. int.): [Mꢂꢃ
Cl] 296
(3); [MꢂꢃC6H5CHO] 225 (63); [Mꢂꢃ
C6H5CHOꢃ
/
7.45 (m, 5H,
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
CH2O] 86 (100). Anal. Found: C, 46.49; H, 5.43; N,
4.65. Calc. for C12H17GeNO4 (311.88): C, 46.21; H,
5.49; N, 4.49%.
CH2O] 195 (41); [N(CH2)2CH2CH2O] 86 (100). Anal.
Found: C, 43.81; H, 4.75; Ge, 21.90. Calc. for
C12H16ClGeNO3 (330.32): C, 43.63; H, 4.88; Ge,
21.98%.
From filtrate the volatiles were evaporated in vacuo.
A precipitate was dried in vacuo. A white solid was
obtained (6.62 g, 26%) as the mixture of 6,
N(CH2CH2O)2(CHPhCH2O)GeOH (7) and 10. 1H-
NMR (CDCl3) for 7: d 1.84 (s, 1H, OH); 2.23 (m,
3.4.2. From reaction of 9 with SOCl2
SOCl2 (0.096 g, 0.8 mmol) was added dropwise to a
solution of 9 (0.31 g, 0.8 mmol) in 6 ml of CHCl3. The
reaction mixture was stirred for 24 h, then the pre-
H6e). 13C-NMR (CDCl3) for 7: atrane C*
47.46, 48.67,
/
56.65, 56.88 59.83, 62.34. Crystals of 7 suitable for X-ray
diffraction study were found in this mixture.
cipitate was filtered off, washed with hexane (3ꢄ
/3 ml)
and dried in vacuo for 2 h. Yield of 3: 0.13 g (49%).
3.7. Synthesis of 1-fluoro-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeF (8)
3.5. Synthesis of 1-(phenylethynyl)-3-phenylgermatrane,
CPh (5)
N(CH2CH2O)2(CH2CHPhO)GeCꢀ
/
A solution of BF3×
/
Et2O (0.15 g, 0.001 mol) in 15 ml of
(EtO)3GeCꢀ
/
CPh (4.4 g, 14 mmol) was added to a
acetonitrile was added to a solution of 6 (1 g, 0.0032
mol) in 20 ml of acetonitrile at 50 8C. After 1 h the solid
solution of product A (2.9 g, 13 mmol) in 50 ml of

18
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
precipitated. After removal of volatile in vacuo hexane
was added to the residue. The precipitate was filtered off
matic protons). 13C-NMR (CDCl3): atrane C*
53.02, 53.05, 53.58, 57.01, 57.11, 57.14, 57.20, 59.21,
59.63, 68.51, 68.52 (C-3); aromatic C*125.74, 125.76,
125.63, 127.15, 127.23, 128.07, 128.11, 142.27, 142.76
(two diastereomers). EI-MS m/e (rel. int.): [Mꢂꢃ
C6H5CHO] 500 (35); [Mꢂꢃ
C6H5CHOꢃCH2O] 470
(28); [Mꢂꢃ
C6H5CHOꢃ2CH2OꢃN(CH2)3] 384 (100);
[Mꢂꢃ
OGe(OCHPhCH2)(OCH2CH2)2N] 296 (11).
/
52.53,
and recrystallized from ethanolꢁ
/
water (1:1). Colorless
/
crystals of 8 were obtained in 52% yield. 1H-NMR
(CDCl3): d 2.60, 2.90, 2.99, 3.11, 3.22, 3.85, 4.05, 4.92
(H-3) [8 m, (AA?XX?)2 and ABX systems of
/
/
/
NCH2CH2O and NCH2CHO groups protons]; 7.28ꢁ
7.39 (m, 5H, aromatic protons). 13C-NMR (CDCl3):
atrane C*52.63, 53.16, 57.13, 57.27, 59.02, 68.96 (C-3);
aromatic C*125.52, 128.25, 128.68, 140.93. EI-MS m/e
(rel. int.): [Mꢂ] 315 (8); [MꢂꢃF] 296 (2); [Mꢂꢃ
C6H5CHO] 209 (100); [Mꢂꢃ
C6H5CHOꢃCH2O] 179
(91); [Mꢂꢃ
FꢃC6H5CHOꢃCH2CH2O] 146 (8);
/
/
/
/
/
/
Anal. Found: C, 46.33; H, 5.22; N, 4.26. Calc. for
C24H32Ge2N2O7 (605.74): C, 47.59; H, 5.33; N, 4.62%.
/
/
/
/
/
/
/
/
3.10. Synthesis of 1-bromo-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeBr (11)
[N(CH2)2CH2CH2O] 86 (91). Anal. Found: C, 45.77;
H, 5.29; N, 4.53. Calc. for C12H16FGeNO3 (313.87): C,
45.92; H, 5.14; N, 4.46%.
Me3SiBr (3.06 g, 20 mmol) was added dropwise to a
suspension of 9 (3.84 g, 10 mmol) in 20 ml of xylene. The
reaction mixture was heated at reflux. After 5 min, 9 has
dissolved and after 30 min of stirring formation of a
precipitate was observed. The reaction mixture was
refluxed for additional 20 min. The precipitate was
3.8. Synthesis of 1-trimethylsiloxy-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeOSiMe3 (9)
3.8.1. From reaction of 6 with (Me3Si)2NH
A mixture of 6 (15 g, 48 mmol), (Me3Si)2NH (23 g,
143 mmol) and 100 ml of xylene was heated at reflux for
8 h. The precipitate was filtered off. After cooling of a
filtrate to room temperature (r.t.), white crystals formed
filtered off, washed with hexane (5ꢄ5 ml), dried in
/
1
vacuo to give 3.1 g (83%) of 11. H-NMR (CDCl3): d
2.65, 2.96, 3.13, 3.21, 3.90, 4.06, 4.96 (H-3) [7 m,
(AA?XX?)2 and ABX systems of NCH2CH2O and
which were filtered off, washed with hexane (5ꢄ
/10 ml),
recrystallized from CH2Cl2ꢁhexane and dried in vacuo
/
NCH2CHO groups protons]; 7.27ꢁ
matic protons). EI-MS m/e (rel. int.): [Mꢂꢃ
(10); [MꢂꢃC6H5CHO] 269 (79); [Mꢂꢃ
C6H5CHOꢃ
CH2O] 239 (34); [Mꢂꢃ
BrꢃC6H5CHO] 190 (37);
[Mꢂꢃ CH2O] 160 (32); [Mꢂꢃ
BrꢃC6H5CHOꢃ Brꢃ
C6H5CHOꢃ BrꢃC6H52O]
CH2CH2O] 146 (11); [Mꢂꢃ
130 (5); [N(CH2)2CH2CH2O] 86 (100). Anal. Found: C,
38.19; H, 4.45; N, 3.91. Calc. for C12H16BrGeNO3
(374.77): C, 38.46; H, 4.30; N, 3.74%.
/
7.38 (m, 5H, aro-
to give 2.9 g (16%) of 9. H- and 13C-NMR (CDCl3)
(Tables 1 and 2). EI-MS m/e (rel. int.): [Mꢂꢃ
CH3] 370
(49); [MꢂꢃC6H5CHO] 279 (66); [Mꢂꢃ
C6H5CHOꢃ
CH2O] 249 (27); C6H5CHOꢃ2CH2Oꢃ
[Mꢂꢃ
1
/Br] 296
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
N(CH2)3] 163 (16); [N(CH2)2CH2CH2O] 86 (100).
Anal. Found: C, 46.64; H, 6.69; N, 3.65. Calc. for
C15H25GeNO4Si (384.06): C, 46.91; H, 6.56; N, 3.65%.
/
/
/
3.8.2. From reaction of 6 with Me3SiClꢁEt3N
/
Et3N (0.71 g, 7 mmol) and then Me3SiCl (0.76 g, 7
mmol) were added dropwise to a suspension of 6 (2 g,
6.4 mmol) in 20 ml of CHCl3. Immediately 6 has
dissolved. The reaction mixture was stirred for 24 h at
r.t., then 20 ml of H2O was added, the water layer was
3.11. Synthesis of [1-(3-phenyl)germatranyl]triflate,
N(CH2CH2O)2(CH2CHPhO)GeOTf (12)
Me3SiOTf (0.71 g, 3.2 mmol) was added dropwise
with stirring to a suspension of 9 (0.5 g, 1.3 mmol) in 10
ml of xylene at r.t. Immediately a formation of a
precipitate was observed. A reaction mixture was stirred
for 24 h. After removal of all volatiles in vacuo, 0.57 g
(100%) pure 12 was obtained as a white solid. EI-MS m/
separated and extracted with CHCl3 (3ꢄ
CHCl3 solutions were washed with H2O (5ꢄ
combined CHCl3 extracts were dried with CaCl2, CHCl3
was removed in vacuo; the residue was dried in vacuo to
give 1.61 g (65%) of 9.
/
20 ml). The
30 ml). The
/
e (rel. int.): [Mꢂ] 445 (0.2); [Mꢂꢃ
[Mꢂꢃ CH2O] 309 (94); [Mꢂꢃ
C6H5CHOꢃ
296 (67); [MꢂꢃOSO2CF3] 266 (31); [Mꢂꢃ
OSO2CF3ꢃ
C6H5CHO] 190 (8); [Mꢂꢃ
OSO2CF3ꢃC6H5CH-
Oꢃ OSO2CF3ꢃC6H5CH-
CH2O] 160 (20); [Mꢂꢃ
OꢃCH2CH2O] 146 (38); [N(CH2)2CH2CH2O] 86
(100). Anal. Found: C, 34.97; H, 3.68; N, 2.96. Calc.
for C13H16F3GeNO6S (443.94): C, 35.17; H, 3.63; N,
3.16%.
/
C6H5CHO] 339 (65);
3.9. Synthesis of [N(CH2CH2O)2(CH2CHPhO)Ge]2O
(10)
/
/
/
OSO2CF3]
/
/
/
/
/
6 (0.7 g, 2.24 mmol) was heated in vacuo at 180 8C for
20 h and the water formed was continuously removed.
Yield of 10: 0.65 g (96%), m.p. 294 8C. 1H-NMR
(CDCl3): d 2.39, 2.75, 2.93, 3.03, 3.71, 3.93, 4.82 (H-3)
[7 m, (AA?XX?)2 and ABX systems of NCH2CH2O and
/
/
/
/
NCH2CHO groups protons]; 7.17ꢁ7.42 (m, 10H, aro-
/

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
19
Table 7
Crystal data, data collection and refinement parameters for 5 and 7ꢁ
/9
Empirical formula
Formula weight
Color, habit
C20H21Ge1N1O3 (5)
395.97
colorless prism
C12H17Ge1N1O4 (7)
311.86
colorless block
C12H16F1Ge1N1O3 (8)
313.85
colorless prism
C15H25Ge1N1O4Si1 (9)
384.04
colorless block
Crystal size (mm3)
Crystal system
0.2ꢄ
/
0.2ꢄ
/
0.2
0.5ꢄ
/
0.2ꢄ/0.2
0.25ꢄ/0.25ꢄ/0.25
0.40ꢄ
/
0.30ꢄ0.10
/
monoclinic
Cc
monoclinic
P21/n
monoclinic
P21/c
orthorhombic
Pnma
Space group
Unit cell dimensions
˚
a (A)
17.075(9)
11.263(7)
11.380(8)
123.61(5)
1823(2)
4
6.861(3)
10.234(3)
17.906(5)
98.49(3)
1243.5(7)
4
9.527(2)
10.108(2)
12.976(2)
99.19(2)
1233.5(4)
4
6.8584(1)
10.9075(3)
23.4761(5)
˚
b (A)
˚
c (A)
b (8)
Volume (A )
3
˚
1756.20(7)
4
1.828
Z
Absorption coefficient (mmꢃ1
Scan mode
)
1.699
v/2u
2.470
v
2.496
v/2u
v
u range (8)
Index ranges
2.31ꢁ
205
65k 5
65l 514
2028
2028 [Rint
/
25.97
h 5
13,
2.30ꢁ
85
35
55
4046
2186 [Rint
/
24.98
h 58,
k 512,
l 521
2.17ꢁ
05h 5
05k 5
155l 5
2556
2415 [Rint
/
25.97
11,
12,
15
2.06ꢁ
85
145
315
12353
2212 [Rint
/
27.99
h 59,
k 511,
l 527
ꢃ
/
/
/17,
ꢃ
/
/
/
/
/
ꢃ
/
/
/
ꢃ
/
/
/
ꢃ
/
/
/
/
/
ꢃ
/
/
/
ꢃ/
/
/
ꢃ/
/
/
ꢃ/
/
/
ꢃ/
/
/
Reflections collected
Independent reflections
Data/restraints/parameters
Reflections with
ꢀ/0.000]
ꢀ
/
0.021]
ꢀ
/
0.024]
ꢀ/0.031]
2028/2/226
1927
2105/0/232
1819
2415/0/227
1958
2212/0/154
2054
I ꢁ2s(I)
/
Goodness-of-fit on F2
Final R indices
1.307
1.071
1.024
1.237
R1ꢀ
wR2ꢀ
R1ꢀ0.0300,
wR2ꢀ0.0702
0.012(3)
/0.0274,
R1ꢀ
wR2ꢀ
R1ꢀ0.0406,
wR2ꢀ0.0797
/
0.0290,
R1ꢀ
wR2ꢀ
R1ꢀ0.0451,
wR2ꢀ0.0756
/
0.0324,
R1ꢀ
wR2ꢀ
R1ꢀ0.0502,
wR2ꢀ0.1101
/
0.0467,
[I ꢁ/2s(I)]
/
0.0691
/
0.0751
/0.0715
/
0.1089
R indices (all data)
/
/
/
/
/
/
/
/
Absolute structure
parameter
ꢃ/
ꢁ/
ꢁ/
ꢁ/
Largest diff. peak
ꢃ3
0.415/ꢃ
/
0.441
0.714/ꢃ
/
0.428
0.289/ꢃ
/
0.365
0.500/ꢃ1.110
/
˚
per hole (e A
)
3.12. Synthesis of 1-methoxy-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeOMe (13)
(100). Anal. Found: C, 48.26; H, 5.63; N, 4.15. Calc.
for C13H19GeNO4 (325.90): C, 47.94; H, 5.88; N, 4.30%.
Et3SnOMe (0.14 g, 0.58 mmol) was added dropwise to
a suspension of 11 (0.2 g, 0.53 mmol) in 10 ml of CHCl3.
After 15 min of stirring, a precipitate of 11 has dissolved
and the reaction mixture was stirred for 24 h at r.t.
CHCl3 was evaporated in vacuo. 20 ml of hexane was
3.13. Synthesis of 1-(fluorenyl)-3-phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeC13H9 (14)
A solution of FluLi, prepared from fluorene (0.43 g,
2.6 mmol) and n-BuLi (1.71 ml, 2.7 mmol) as a 1.6-M
solution in hexane, was added to a solution of 9 (1.0 g,
2.6 mmol) in THF (10 ml) at r.t. The reaction mixture
was stirred for 24 h at r.t; all volatiles were evaporated in
vacuo. 20 ml of toluene was added. The white solid was
added, a white solid was filtered off, washed with hexane
1
10 ml) and dried. Yield of 13: 0.16 g (94%). H-
(5ꢄ
/
NMR (CDCl3): d 2.38, 2.74, 2.92, 3.03, 3.63, 3.79, 4.71
(H-3) [7 m, (AA?XX?)2 and ABX systems of
NCH2CH2O and NCH2CHO groups protons]; 3.57 (s,
filtered off, washed with hexane (2ꢄ10 ml) and dried in
/
1
7.27 (m, 5H, aromatic protons). 13C-
52.21, 52.77,
125.46,
vacuo. Yield of 14: 0.73 g (61%). H-NMR (CDCl3): d
2.34, 2.64, 2.85, 2.95, 3.55, 3.61, 3.72, 3.80, 4.72 (H-3) [9
m, (AA?XX?)2 and ABX systems of NCH2CH2O and
3H, OMe); 7.14ꢁ
NMR (CDCl3): 53.03 (OMe); atrane C*
56.78, 56.87, 58.73, 68.37 (C-3); aromatic C*
127.83, 128.45, 141.06. EI-MS m/e (rel. int.): [Mꢂꢃ
OMe] 296 (6); [MꢂꢃC6H5CHO] 221 (31); [Mꢂꢃ
OCH3ꢃC6H5CHO] 190 (17); OCH3ꢃ
[Mꢂꢃ
C6H5CHOꢃ OCH3ꢃC6H5-
CH2O] 160 (22); [Mꢂꢃ
CHOꢃ OCH3ꢃ
CH2CH2O] 146 (19); 130 [Mꢂꢃ
C6H5CHOꢃ2CH2O] (8); [N(CH2)2CH2CH2O] 86
/
/
/
NCH2CHO groups protons]; 4.20 (s, 1H, CHGe); 7.23ꢁ
7.33, 7.79ꢁ7.84, 7.93ꢁ7.97 (3 m, 13H, aromatic pro-
tons). 13C-NMR (CDCl3): 44.82 (CGe); atrane C*
52.25, 52.79, 56.97, 57.08, 58.80, 68.27 (C-3); aromatic
C*119.42, 125.19, 125.42, 125.72, 125.90, 127.48,
128.41, 140.91, 142.54, 145.32. EI-MS m/e (rel. int.):
[Mꢂ] 461 (3); [MꢂꢃC13H9] 296 (100), [Mꢂꢃ
C13H9ꢃ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

20
E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ21
/
C6H5CHO] 190 (13); [Mꢂꢃ
CH2CH2O] 146 (19). Anal. Found: C, 65.42; H, 5.42;
N, 2.91. Calc. for C25H25GeNO3 (460.08): C, 65.26; H,
5.48; N, 3.04%.
/
C13H9ꢃ
/
C6H5CHOꢃ
/
Data Centre, CCDC No. 191521 for compound 5,
CCDC No. 191522 for compound 7, CCDC No.
191523 for compound 8, CCDC No. 196131 for
compound 9. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
3.14. Synthesis of 1-[bis(trimethylsilyl)amino]-3-
phenylgermatrane,
N(CH2CH2O)2(CH2CHPhO)GeN(SiMe3)2 (15)
Union Road, Cambridge, CB2 1EZ, UK (Fax. ꢂ44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk).
/
A solution of (Me3Si)2NLi, prepared from (Me3-
Si)2NH (0.22 g, 1.36 mmol) and n-BuLi (0.88 ml, 1.4
mmol) as a 1.66-M solution in hexane, was added to a
suspension of 11 (0.5 g, 1.33 mmol) in 10 ml of THF at
r.t. The reaction mixture was stirred for 24 h at r.t;
volatiles were evaporated in vacuo and then 20 ml of
toluene was added. The white solid was filtered off,
Acknowledgements
We thank Dr. A.V. Yatsenko for the X-ray crystal
structure determination of 5 and 8. This work was
supported by INTAS under Grant No. YSF-2001/2-135
for S.S.K., by the Fonds der Deutschen Chemischen
Industrie (VCI) for J.L. as well as by the Russian
Foundation for Basic Research under Grant Nos. 01-03-
32474 and 02-03-06347. A.V.C. is grateful to the Royal
Society of Chemistry for the RSC Journal Grants for
International Authors.
washed with hexane (2ꢄ10 ml) and dried in vacuo.
/
1
Yield of 15: 0.28 g (46%). H-NMR (C6D6): d 0.62 (s,
18H, Me3Si); 1.89, 1.98, 2.14, 2.29, 3.38, 3.53, 4.58 (H-3)
[7 m, (AA?XX?)2 and ABX systems of NCH2CH2O and
NCH2CHO groups protons]; 7.18ꢁ
matic protons). 13C-NMR (CDCl3): 5.45 (Me3Si); atrane
C*52.90, 53.37, 57.19, 57.29, 59.94, 69.40 (C-3);
aromatic C*125.91, 127.71, 128.00, 142.57. EI-MS m/
(rel. int.): [MꢂꢃMe] 441 (100); [Mꢂꢃ
CH3ꢃ
C6H5CHO] 335 (23); [Mꢂꢃ
N(SiMe3)2] 296 (1.8);
[Mꢂꢃ 2CH2ON(CH2)3] 234 (30); [Mꢂꢃ
C6H5CHOꢃ
C6H5CHOꢃCH2CH2OꢃN(SiMe3)2] 146 (44);
/7.44 (m, 5H, aro-
/
/
e
/
/
/
References
/
[1] S.S. Karlov, G.S. Zaitseva, Chem. Heterocycl. Comp. 37 (2001)
1325.
/
/
/
/
/
[2] I.B. Mazheika, A.P. Gaukhman, I.I. Solomennikova, A.F.
Lapsinya, I.P. Urtane, G.I. Zelchan, E.Ya. Lukevics, Zh. Obshch.
Khim. 54 (1984) 123.
[HN(CH2CH2O)2CH2CH] 130 (93). Anal. Found: C,
47.62; H, 7.42; N, 6.01. Calc. for C18H34GeN2O3Si2
(455.26): C, 47.49; H, 7.53; N, 6.15%.
[3] M.G. Voronkov, Z.A. Ochinnikova, V.P. Baryshok, Zh. Obshch.
Khim. 57 (1987) 2643.
[4] E. Lukevics, S. Belyakov, O. Pudova, J. Organomet. Chem. 523
(1996) 41.
3.15. X-ray crystallographic study of 5 and 7ꢁ9
/
[5] W.S. Emerson, E.P. Agnew, J. Am. Chem. Soc. 67 (1945) 516.
[6] Yu.E. Ovchinnikov, Yu.T. Struchkov, V.P. Baryshok, Z.A.
Ovchinnikova, M.G. Voronkov, Dokl. Akad. Nauk. SSSR 330
(1993) 464.
Table 7 summarizes the crystal data as well as details
of data collection and structure determination for
compounds 5 and 7ꢁ9. The experimental data for 5, 7
/
[7] S.S. Karlov, P.L. Shutov, N.G. Akhmedov, M.A. Seip, J.
Lorberth, G.S. Zaitseva, J. Organomet. Chem. 598 (2000) 387.
[8] M.G. Voronkov, Z.A. Ovchinnikova, V.P. Baryshok, Izv. Akad.
Nauk. SSSR, Ser. Khim. (1987) 880.
and 8 were collected on an Enraf-Nonius CAD4
diffractometer at room temperature using graphite
˚
monochromatized MoꢁKa radiation (0.71073 A). As
/
for 9, intensities were measured on Bruker SMART
CCD diffractometer at 120 K. All structures were solved
by direct methods (SHELXS-86 [29]) and refined by full-
matrix least-squares based on F2 with anisotropic
thermal parameters for all non-hydrogen atoms
[9] V.F. Mironov, T.K. Gar, N.Yu. Khromova, O.D. Frid, Zh.
Obshch. Khim. 56 (1986) 638.
[10] M. Nasim, L.I. Livantsova, D.P. Krut’ko, G.S. Zaitseva, V.S.
Petrosyan, Vestn. MGU, Ser. 2, Khim. 31 (1990) 289 [Chem.
Abstr. 114 (1991) 81986y].
[11] M. Nasim, L.I. Livantsova, G.S. Zaitseva, J. Lorberth, J.
Organomet. Chem. 403 (1991) 85.
(
SHELXL-97 [30]). For structures 7 and 8, all hydrogen
[12] P. Rivie`re, M. Rivie`re-Baudet, J. Satge´, in: G. Wilkinson, F.
Gordon, A. Stone, E. Abel (Eds.), Comprehensive Organometal-
lic Chemistry I, Vol. 2, Pergamon Press, Oxford, p. 399.
[13] W. Uhlig, J. Organomet. Chem. 409 (1990) 377.
[14] M. Tasaka, M. Hirostu, M. Kojima, Inorg. Chem. 35 (1996) 6981.
[15] T.K. Gar, N.Yu. Khromova, S.N. Tandura, V.N. Bochkarev,
A.E. Chernyshev, V.F. Mironov, Zh. Obshch. Khim. 52 (1982)
2579.
atoms were found from difference Fourier synthesis and
refined isotropically. In the structures of 5 and 9,
hydrogen atoms were placed in calculated positions
and refined using a riding model.
4. Supplementary material
[16] A.Yu. Chervinskii, M.Yu. Zubritskii, L.M. Kapkan, Ukr. Khim.
Zh. 60 (1994) 440.
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
[17] M.G. Voronkov, S.N. Tandura, B.Z. Shterenberg, A.L. Kuznet-
sov, R.G. Mirskov, G.I. Zelchan, N.Yu. Khromova, T.K. Gar,

E.V. Gauchenova et al. / Journal of Organometallic Chemistry 676 (2003) 8ꢁ
/21
21
V.F. Mironov, V.A. Pestunovich, Dokl. Akad. Nauk. SSSR 248
(1944) 134.
[23] S.P. Narula, S. Soni, R. Shankar, R.K. Chadha, J. Chem. Soc.
Dalton Trans. (1992) 3055.
[18] G.S. Zaitseva, S.S. Karlov, A.V. Churakov, J.A.K. Howard, E.V.
Avtomonov, J. Lorberth, Z. Anorg. Allg. Chem. 623 (1999)
1144.
[24] S.N. Gurkova, S.N. Tandura, A.V. Kisin, A.I. Gusev, N.V.
Alekseev, T.K. Gar, N.Yu. Khromova, I.R. Segel’man, Zh.
Strukt. Khim. 23 (1982) 101.
[19] G.S. Zaitseva, S.S. Karlov, B.A. Siggelkow, E.V. Avtomonov,
A.V. Churakov, J.A.K. Howard, J. Lorberth, Z. Naturforsch. B
53 (1998) 1247.
[25] S.N. Gurkova, A.I. Gusev, N.V. Alekseev, T.K. Gar, N.Yu.
Khromova, Zh. Strukt. Khim. 26 (1995) 154.
[26] E. Lukevics, S. Belyakov, L. Ignatovich, N. Shilina, Bull. Soc.
Chim. Fr. 132 (1995) 545.
[20] G.S. Zaitseva, S.S. Karlov, G.V. Pen’kovoy, A.V. Churakov,
J.A.K. Howard, B.A. Siggelkow, E.V. Avtomonov, J. Lorberth,
Z. Anorg. Allg. Chem. 625 (1999) 655.
[27] E. Lukevics, P. Arsenyan, S. Belyakov, O. Pudova, Main Group
Met. Chem. 24 (2001) 253.
[21] S.S. Karlov, P.L. Shutov, A.V. Churakov, J. Lorberth, G.S.
Zaitseva, J. Organomet. Chem. 627 (2001) 1.
[28] H. Gilman, A.H. Haubein, J. Am. Chem. Soc. 66 (1944) 1515.
[29] G.M. Sheldrick, Acta Crystallogr. Sect. A 46 (1990) 467.
[30] G.M. Sheldrick, SHELXL-97: Program for the Refinement of
[22] R. Eujen, E. Petrauskas, A. Roth, D.J. Brauer, J. Organomet.
Chem. 613 (2000) 86.
Crystal Structures, University of Gottingen, Germany, 1997.
¨