Azametallatranes of group 14 elements. Syntheses and X-ray studies

Article abstract of DOI:10.1021/om020708h

Syntheses of a series of the title compounds, viz., N(CH₂CH₂NR)₃M-X (1, M = Si, X = Me, R = SiMe₃; 2, M = Si, X = Et, R = SiMe₃; 3, M = Si, X = n-Bu, R = SiMe₃; 4, M = Si, X = vinyl, R = SiMe₃; 5, M = Si, X = Ph, R = SiMe₃; 6, M = Ge, X = Me, R = SiMe₃; 7, M = Ge, X = n-Bu, R = SiMe₃; 8, M = Ge, X = Ph, R = SiMe₃; 9, M = Sn, X = n-Bu, R = SiMe₃; 10, M = Sn, X = Ph, R = SiMe₃; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me, R = Me) by the reaction of X-MCl₃ with N(CH₂CH₂NSiMe₃Li)₃ or with N(CH₂CH₂NMeLi)₃ are reported. Reactions of the novel compounds X-Ge(NMe₂)₃ (15, X = Ph; 16, X = 1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH₂CH₂NHMe)₃ or N(CH₂-CH₂NH₂)₃ resulted in new 1-arylazagermatranes, N(CH₂CH₂NMe)₃Ge-X (19, X = Ph; 20, X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH₂CH₂NH)₃Ge-X (23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazagermatrane (23) is transformed to 8 by treatment with n-BuLi/Me₃SiCl. Composition and structures of novel compounds were established by elemental analyses, ¹H, ¹³C, and ²⁹Si NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly indicated the presence of a transannular interaction M←N_ax for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M←N_ax distances.

Full text of DOI:10.1021/om020708h

516
Organometallics 2003, 22, 516-522
Aza m eta lla tr a n es of Gr ou p 14 Elem en ts. Syn th eses a n d
X-r a y Stu d ies
Pavel L. Shutov,† Denis A. Sorokin,‡ Sergey S. Karlov,*,‡ Klaus Harms,†
Yuri F. Oprunenko,‡ Andrei V. Churakov,§ Mikhail Yu. Antipin,#
Galina S. Zaitseva,‡ and J o¨rg Lorberth*,†
Fachbereich Chemie, Philipps-Universita¨t Marburg, Hans-Meerwein-Strasse,
D-35032 Marburg/ Lahn, Germany, Chemistry Department, Moscow State University,
B-234 Leninskie Gory, 119899 Moscow, Russia, N. S. Kurnakov Institute of General and
Inorganic Chemistry RAS, Leninskii pr. 31, 119991, Moscow, Russia, and A. N. Nesmeyanov
Institute of Organoelement Compounds RAS, Vavilova str. 28, 119991, Moscow, Russia
Received August 29, 2002
Syntheses of a series of the title compounds, viz., N(CH2CH2NR)3M-X (1, M ) Si, X )
Me, R ) SiMe3; 2, M ) Si, X ) Et, R ) SiMe3; 3, M ) Si, X ) n-Bu, R ) SiMe3; 4, M ) Si,
X ) vinyl, R ) SiMe3; 5, M ) Si, X ) Ph, R ) SiMe3; 6, M ) Ge, X ) Me, R ) SiMe3; 7, M
) Ge, X ) n-Bu, R ) SiMe3; 8, M ) Ge, X ) Ph, R ) SiMe3; 9, M ) Sn, X ) n-Bu, R )
SiMe3; 10, M ) Sn, X ) Ph, R ) SiMe3; 11, M ) Si, X ) vinyl, R ) Me; 12, M ) Ge, X ) Me,
R ) Me) by the reaction of X-MCl3 with N(CH2CH2NSiMe3Li)3 or with N(CH2CH2NMeLi)3
are reported. Reactions of the novel compounds X-Ge(NMe2)3 (15, X ) Ph; 16, X )
1-naphthyl; 17, X ) 9-antracenyl; 18, X ) 9-phenantrenyl) with N(CH2CH2NHMe)3 or N(CH2-
CH2NH2)3 resulted in new 1-arylazagermatranes, N(CH2CH2NMe)3Ge-X (19, X ) Ph; 20,
X ) 1-naphthyl; 21, X ) 9-antracenyl; 22, X ) 9-phenantrenyl) and N(CH2CH2NH)3Ge-X
(23, X ) Ph; 24, X ) 1-naphthyl; 25, X ) 9-phenantrenyl), respectively. 1-Phenylazager-
matrane (23) is transformed to 8 by treatment with n-BuLi/Me3SiCl. Composition and
1
structures of novel compounds were established by elemental analyses, H, 13C, and 29Si
NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly
indicated the presence of a transannular interaction MrNax for both compounds. quasi-
Azametallatranes 5 and 8 possess extremely long MrNax distances.
In tr od u ction
chemistry by varying the substitution pattern at both
the metal center and the equatorial nitrogen substitu-
ents in B.5
Among azametallatranes of the group 14 elements
azasilatranes (B, M ) Si), first prepared by Le Grow in
1971, are the most extensively studied.9-22 Azastan-
The structure and chemical behavior of metallatranes,
N(CH2CH2O)3M-X (A)scyclic derivatives of trialkanol-
aminesshave been extensively studied,1-4 and com-
pounds of elements have been reported all over the
periodic table. By contrast, azametallatranes, N(CH2-
CH2NR)3M-X (B), which are the product of a formal
substitution of the oxygen atoms in molecule (A) by NR
groups, are less well-known;1,4,5 however, interest in
azametallatranes (B) has grown steadily over the two
past decades: one of the reasons is their potential
application as MOCVD precursors for metal and non-
metal nitrides,1,6-8 and another is their wide scope of
(7) Pinkas, J .; Wang, T.; J acobson, R. A.; Verkade, J . G. Inorg. Chem.
1994, 33, 4202-4210.
(8) Pinkas, J .; Wang, T.; J acobson, R. A.; Verkade, J . G. Inorg. Chem.
1994, 33, 5244-5253.
(9) Pat. USA 3,576,26, 1971.
(10) Lukevics, E.; Zelchan, G. I.; Solomennikova, I. I.; Liepin’sh, E.;
Yankovska, I. S.; Mazheika, I. B. J . Gen. Chem. USSR (Engl. Transl.)
1977, 47, 98-101.
(11) Kupcˇe, Eh.; Liepin¸ sˇ, E.; Lapsin¸ a, A.; Zelcˇajns, G.; Lukevics, E. J .
Organomet. Chem. 1987, 333, 1-7.
(12) Macharashvili, A. A.; Shklover, V. E.; Struchkov, Yu. T.;
Lapsina, A.; Zelcans, G.; Lukevics, E. J . Organomet. Chem. 1988, 349,
23-27.
* Corresponding authors. (J .L.) Fax: +49 (0)6421-282-5642. E-
mail: lorberth@chemie.uni-marburg.de. (S.S.K.) Fax: +7(095)9328846.
E-mail: sergej@org.chem.msu.su.
(13) Gudat, D.; Verkade, J . G. Organometallics 1989, 8, 2772-2779.
(14) Gudat, D.; Daniels, L. M.; Verkade, J . G. J . Am. Chem. Soc.
1989, 111, 8520-8522.
† Philipps-Universita¨t Marburg.
‡ Moscow State University.
(15) Gudat, D.; Daniels, L. M.; Verkade, J . G. Organometallics 1990,
9, 1464-1470.
§ N. S. Kurnakov Institute of General and Inorganic Chemistry RAS.
#
A. N. Nesmeyanov Institute of Organoelement Compounds RAS.
(16) Gudat, D.; Verkade, J . G. Organometallics 1990, 9, 2172-2175.
(17) Woning, J .; Daniels, L. M.; Verkade, J . G. J . Am. Chem. Soc.
1990, 112, 4601-4602.
(1) Verkade, J . G. Coord. Chem. Rev. 1994, 137, 233-295.
(2) Pestunovich, V.; Kirpichenko, S.; Voronkov M. In The Chemistry
of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; J ohn
Wiley & Sons: New York, 1998; Vol. 2, Part 1, Chapter 24.
(3) Holmes, R. R. Chem. Rev. 1996, 96, 927-950.
(4) Karlov, S. S.; Zaitseva, G. S. Chem. Heterocycl. Comp. 2001, 37,
1325-1357.
(5) Schrock, R. R. Acc. Chem. Res. 1997, 30, 9-16.
(6) Pinkas, J .; Gaul, B.; Verkade, J . G. J . Am. Chem. Soc. 1993, 115,
3925-3931.
(18) Woning, J .; Verkade, J . G. J . Am. Chem. Soc. 1991, 113, 944-
949.
(19) Woning, J .; Verkade, J . G. Organometallics 1991, 10, 2259-
2266.
(20) Wan, Y.; Verkade, J . G. Organometallics 1994, 13, 4164-4166.
(21) Wan, Y.; Verkade, J . G. J . Am. Chem. Soc. 1995, 117, 141-
156.
(22) Wan, Y.; Verkade, J . G. Organometallics 1996, 15, 5769-5771.
10.1021/om020708h CCC: $25.00 © 2003 American Chemical Society
Publication on Web 12/28/2002

Azametallatranes of Group 14 Elements
Organometallics, Vol. 22, No. 3, 2003 517
natranes (B, M ) Sn) and especially azagermatranes
(B, M ) Ge) are quite rare.23-28 In contrast to metal-
latranes,1,4,29,30 the structure of azametallatranes of the
group 14 elements was rarely explored by X-ray diffrac-
tion studies.
at room temperature led to azametallatranes 1-10 in
good yields (eq 1). The reaction of Li3-Me-tren with
X-MCl3 is less specific. We prepared azaatranes 11 and
12 as colorless liquids only in minor yields by the
reaction of Li3-Me-tren with vinyl-SiCl3 and Me-GeCl3,
respectively (eq 1). Li3-Me3Si-tren and Li3-Me-tren were
generated in situ by treatment of Me3Si-tren (13) and
Me-tren (14) with 3 equiv of n-BuLi, respectively.
As a part of our program to investigate the chemical
behavior of both metallatranes and azametallatranes
and the degree of strength of the transannular MrN
interactions in these compounds,31-40 we recently re-
ported a new approach to 1-haloazagermatranes and
1-haloazastannatranes, viz., treatment of MHal4 (M )
Ge, Sn) with N(CH2CH2NMeLi)3 (Li3-Me-tren) and with
N(CH2CH2NSiMe3Li)3 (Li3-Me3Si-tren).41 In this report
we present the use of lithium salts Li3-Me-tren and Li3-
Me3Si-tren in metathetical reactions of these salts with
X-MCl3 (M ) Si, Ge, Sn) for the synthesis of 1-alkyl-,
1-vinyl-, and 1-arylazametallatranes of the group 14
elements. A number of 1-arylazagermatranes were
obtained by transamination reactions between X-M-
(NMe2)3 and N(CH2CH2NHR)3. The 29Si NMR spectra
of these compounds are discussed. X-ray structural
investigations of four azametallatranes are presented.
It should be noted that the M-N contact distance in
atranes is influenced by the nature of the metal, the
electronic and steric properties of the apical substituent
on the metal atom, and, of course, the structure of the
atrane moiety. Motivation in our work was to study
structural changes in azametallatranes arising from
both the formal replacement of NMe or NH groups with
NSiMe3 groups in the azaatrane skeleton and the nature
of apical substituents on the metal atom.
Due to small yields of azametallatranes 11 and 12
[N(CH2CH2NMe)3M-X], obtained from the reaction of
Li3-Me-tren with X-MCl3, the usual approach to
azametallatranesstransamination reaction (eq 2)swas
used for preparation of 1-aryl-N,N′N′′-trimethylazager-
matranes (19-22). Tetraamine 14 reacts in several
hours with X-Ge(NMe2)3 (X ) phenyl (15); 1-naphthyl
(16); 9-antracenyl (17); 9-phenantrenyl (18)) at high
temperature without any solvent. The starting materi-
als 15-18, also unknown before, were readily synthe-
sized by an exchange reaction between lithium or
magnesium derivatives and Cl-Ge(NMe2)3. In a similar
manner transamination reactions of X-Ge(NMe2)3 (15,
16, 18) with the tetraamine 26 [N(CH2CH2NH2)3, tren]
lead to the formation of azagermatranes 23-25 in
satisfactory yields (eq 2). In contrast, reaction of tris-
amide 17 with tren 26 gives after workup procedure
only polymeric products. Although Verkade et al. have
demonstrated that transamination reactions between
X-Ge(NMe2)3 and 14 in the case of X ) Me, tert-Bu
demand the presence of a catalyst,23 we have shown that
it is not necessary in transamination reactions of
aryltris(dimethylamino)germanes with the tetraamine
14.
Resu lts a n d Discu ssion
The smooth reaction of X-MCl3 (M ) Si, Ge, Sn; X )
organyl substituent) with Li3-Me3Si-tren during 24 h
(23) Wan, Y.; Verkade, J . G. Inorg. Chem. 1993, 32, 79-81.
(24) Plass, W.; Verkade, J . G. J . Am. Chem. Soc. 1992, 114, 2275-
2276.
(25) Plass, W.; Verkade, J . G. Inorg. Chem. 1993, 32, 3762-3765.
(26) Plass, W.; Verkade, J . G. Inorg. Chem. 1993, 32, 5145-5152.
(27) Plass, W.; Verkade, J . G. Inorg. Chem. 1993, 32, 5153-5159.
(28) Plass, W.; Pinkas, J .; Verkade, J . G. Inorg. Chem. 1997, 36,
1973-1978.
(29) Greenberg, A.; Wu, G. Struct. Chem. 1990, 1, 79-85.
(30) Hencsei, P. Struct. Chem. 1991, 2, 21-26.
(31) Zaitseva, G. S.; Karlov, S. S.; Churakov, A. V.; Avtomonov, E.
V.; Lorberth. J .; Hertel, D. J . Organomet. Chem. 1996, 523, 221-225.
(32) Zaitseva, G. S.; Karlov, S. S.; Alekseyeva, E. S.; Aslanov, L. A.;
Avtomonov, E. V.; Lorberth, J . Z. Naturforsch. 1997, 52b, 30-34.
(33) Zaitseva, G. S.; Karlov, S. S.; Churakov, A. V.; Howard, J . A.
K.; Avtomonov, E. V.; Lorberth, J . Z. Anorg. Allg. Chem. 1997, 623,
1144-1150.
(34) Zaitseva, G. S.; Livantsova, L. I.; Nasim, M.; Karlov, S. S.;
Churakov, A. V.; Howard, J . A. K.; Avtomonov, E. V.; Lorberth, J .
Chem. Ber. 1997, 130, 739-746.
(35) Zaitseva, G. S.; Siggelkow, B. A.; Karlov, S. S.; Pen’kovoy, G.
V.; Lorberth, J . Z. Naturforsch. 1998, 53b, 1255-1258.
(36) Zaitseva, G. S.; Karlov, S. S.; Siggelkow, B. A.; Avtomonov, E.
V.; Churakov, A. V.; Howard, J . A. K.; Lorberth, J . Z. Naturforsch.
1998, 53b, 1247-1254.
(37) Zaitseva, G. S.; Karlov, S. S.; Pen’kovoy, G. V.; Churakov, A.
V.; Howard, J . A. K.; Siggelkow, B. A.; Avtomonov, E. V.; Lorberth, J .
Z. Anorg. Allg. Chem. 1999, 625, 655-660.
(38) Karlov. S. S.; Shutov. P. L.; Akhmedov, N. G.; Seip, M. A.;
Lorberth, J .; Zaitseva, G. S. J . Organomet. Chem. 2000, 598, 387-
394.
(39) Karlov, S. S.; Shutov, P. L.; Churakov, A. V.; Lorberth, J .;
Zaitseva, G. S. J . Organomet. Chem. 2001, 627, 1-5.
(40) Shutov, P. L.; Karlov, S. S.; Lorberth, J .; Zaitseva, G. S. Z.
Naturforsch. 2001, 56b, 137-140.
(41) Shutov, P. L.; Karlov, S. S.; Harms, K.; Churakov, A. V.;
Howard, J . A. K.; Lorberth, J .; Zaitseva, G. S. Eur. J . Inorg. Chem.
2002, 2784-2788.
We also studied an alternative approach for the
formation of azagermatranes containing trimethylsilyl
substituents at the equatorial nitrogen atoms, viz.,
silylation reactions of azagermatranes N(CH2CH2-
NH)3Ge-X with a n-BuLi/Me3SiCl system (eq 3). The

518 Organometallics, Vol. 22, No. 3, 2003
Shutov et al.
Ta ble 1. Cr ysta l Da ta , Da ta Collection , Str u ctu r e Solu tion , a n d Refin em en t P a r a m eter s for 5, 8, 10, a n d 19
5
8
10
19
empirical formula
fw
C
21H44N4Si4
C
21H44GeN4Si3
C
21H44N4Si3Sn
C15H26GeN4
334.99
464.96
509.46
555.56
color, habit
plate, colorless
0.60 × 0.30 × 0.21
rhombohedral
R3c, Z ) 18
a ) 20.3499(9)
b ) 20.3499(9)
c ) 34.489(3)
R ) 90
prism, colorless
0.35 × 0.25 × 0.18
rhombohedral
R3c, Z ) 18
a ) 20.3810(6)
b ) 20.3810(6)
c ) 34.732(2)
R ) 90
nugget,colorless
0.48 × 0.30 × 0.27
triclinic
block, colorless
0.40 × 0.30 × 0.20
orthorhombic
P212121, Z ) 4
a ) 8.3466(6)
b ) 11.2962(8)
c )16.363(1)
R ) 90
crystal size [mm]
crystal system
space group, Z
unit cell dimens [Å and deg]
P1h, Z ) 4
a ) 10.7581(8)
b ) 16.267(1)
c ) 17.826(1)
R ) 73.644(6)
â ) 88.022(6)
γ ) 72.245(5)
2846.3(4)
â ) 90
â ) 90
â ) 90
γ ) 120
12368.9(12)
1.124
0.231
4572
γ ) 120
12494.4(7)
1.219
1.247
4896
γ ) 90
1542.8(2)
1.442
1.983
volume [Å3]
density (calc), [g cm-3
]
1.296
1.038
1160
abs coeff [mm-1
F(000)
]
704
diffractometer
Stoe IPDS
193(2)
Stoe IPDS
193(2)
Stoe IPDS-II
Bruker SMART
110(2)
temperature [K]
radiation [λ, Å]
θ-range [deg]
index ranges
193(2)
graphite monochromatized Mo KR, 0.71073
2.60 to 25.96
-24 e h e 24
-24 e k e 24
-42 e l e 42
28 420
5323 [Rint ) 0.0456]
Stoe Integrate46a
none
2.00 to 25.90
-24 < h e 24
-25 e k e 25
-42 e l e 42
38 778
5389 [Rint ) 0.0567]
Stoe Integrate46a
none
1.37 to 24.92
-12 e h e 12
-19 e k e 19
-21 e l e 21
36 345
9878 [Rint ) 0.0469]
Stoe WinIntegrate46b
none
2.19 to 26.99
-11 < h e 11
-15 e k e 15
-23 e l e 13
11 023
3369 [Rint ) 0.0746]
Bruker SAINT45a
SADABS45b
0.4298/1.0000
3347/0/284
1.033
no. of reflns collected
no. of ind reflns
data reduction
abs corr
min./max. transmn
no. of data/restraints/param
5323/1/272
0.987
5389/1/271
0.921
9878/0/541
0.952
GOOF on F2
R1 [I > 2σ(I)]
wR2 (all data)
0.0272
0.0656
0.0257
0.0532
0.0204
0.0508
0.0383
0.0956
Flack param
0.00(7)
0.217/-0.172
-0002(6)
0.248/-0.342
-0.02(1)
1.193/-1.168
largest diff peak and hole [e Å-3
]
0.537/-0.563
small yield in the reaction above (1H NMR spectroscopy
data) is probably due to steric hindrance in azager-
matrane 23 in comparison with that of N(CH2CH2-
NH)3Si-Me, which recently was used as a starting
material for the synthesis of azasilatrane 1.14
[M ) Si (5), Ge (8), Sn (10)] and N(CH2CH2NMe)3Ge-
C6H5 (19). Table 2 summarizes crystal data as well as
details of the data collection and structure refinement
for compounds 5, 8, 10, and 19.43-46
Important bond lengths and angles for studied com-
pounds are summarized in Table 2.The primary coor-
dination environment at the Si(1) atom in 5 is formed
by three covalently linked nitrogen atoms [Neq: N(1),
N(7), N(10)] and the carbon atom C(11) and may be
regarded as tetrahedral. Similarly, the coordination
polyhedron at the germanium atom in 8 represents a
slightly distorted tetrahedron with [Neq: N(1), N(3),
N(4)] and C(7) atoms in the vertexes. However, both
compounds may also be considered as the derivatives
of pentacoordinated silicon and germanium with weak
MrNax interactions based on the following intramo-
lecular distances [N(4)-Si(1) (2.792(1) Å) for 5 and
N(2)-Ge(1) (2.766(2) Å) for 8]. The latter values are
considerably shorter than the sum of the van der Waals
radii of Si and N (3.65 Å) and Ge and N (3.75 Å),
respectively.47 According to Verkade, these compounds
have to be treated as quasi-azametallatranes.1 The
distances differ from the typical ranges for “normal”
azasilatranes (2.034(2)-2.214(3) Å)15,21 and azager-
matranes (2.167(4)-2.278(2) Å).41 A similar long dis-
tance SirNax was previously only found in the single
N,N′N′′-Tris(trimethylsilyl)azasilatranes 2-5 were
investigated by 29Si NMR spectroscopy to establish the
structure of these compounds in solution. The δ 29Sicentral
values (C6D6) of 2-5 [-24.7-(-21.4) ppm] shift to low
field as compared with related N,N′N′′-trimethylaza-
silatranes [-44.4-(-40.9) ppm].21 In general, this fact
underlines the decrease of coordination number at the
silicon atom.42 Consequently, the transannular Sicentral
r Nax interaction in N,N′N′′-tris(trimethylsilyl)aza-
silatranes 2-5 in solution is weaker than that in the
related N,N′N′′-trimethylazasilatranes.
The same trend of weakness of this interaction for
azametallatranes of the group 14 elements is observed
in the solid state. To the best of our knowledge,
compound 1 was the only one to be structurally char-
acterized by X-ray studies14 among the N(CH2CH2-
NSiMe3)3Si-X series prior to our investigations. Re-
cently we have prepared and characterized by X-ray
analysis N(CH2CH2NSiMe3)3Ge-Cl.41 Herein we report
the crystal structures of N(CH2CH2NSiMe3)3M-C6H5
(43) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467-473.
(44) Sheldrick, G. M. SHELXL-97, Program for the Refinement of
Crystal Structures; University of Go¨ttingen: Germany, 1997.
(45) (a)SAINT Version 5.0; Bruker AXS Inc.: Madison, WI, 1997.
(b) SHELXTL Version 5.0; Bruker AXS Inc.: Madison, WI, 1997.
(46) (a)Stoe-Integrate STOE IPDS Software Version 2.90; STOE &
CIE GmbH: Darmstadt, 1999. (b) Stoe Win-Integrate STOE X-Area
Version 1.15; STOE & CIE GmbH: Darmstadt, 2001.
(42) Tandura, S. N.; Voronkov, M. G.; Alekseev, N. V. Top. Curr.
Chem. 1986, 131, 99-189.
(47) Bondi, A. J . Phys. Chem. 1964, 68, 441-451.

Azametallatranes of Group 14 Elements
Organometallics, Vol. 22, No. 3, 2003 519
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 5, 8, 10, a n d 19, N(CH2CH2NR)3M-C6H5
10; M ) Sn, R ) SiMe3
5; M ) Si, R ) SiMe3
8; M ) Ge, R ) SiMe3
molecule A
molecule B
19; M ) Ge, R ) Me
MrNax
M-Neq
2.792(1)
1.743(1)
1.750(1)
1.753(1)
1.910(2)
0.50
2.766(2)
1.850(2)
1.855(2)
1.862(2)
1.985(2)
0.54
2.509(2)
2.057(2)
2.061(1)
2.064(2)
2.172(2)
0.51
2.523(2)
2.052(2)
2.054(2)
2.057(2)
2.169(2)
0.51
2.307(2)
1.869(2)
1.879(3)
1.890(2)
1.984(2)
0.32
M-CPh
∆Ma
b
∆Nax
0.17
176.2
0.22
176.4
0.38
0.38
0.38
Nax-M-CPh
Neq-M-Neq
172.50(6)
112.10(6)
111.38(6)
118.89(6)
110.25(6)
98.71(6)
104.17(6)
114.0(2)
113.2(1)
113.3(2)
172.39(7)
113.56(8)
117.64(7)
110.98(7)
100.18(7)
111.24(7)
101.90(7)
113.6(2)
113.8(2)
113.5(2)
176.15(9)
120.4(1)
115.3(1)
115.8(1)
98.0(1)
101.6(1)
99.8(1)
114.7(2)
113.1(3)
112.8(2)
113.74(6)
111.96(6)
110.87(6)
103.75(6)
107.46(6)
108.60(6)
118.8(2)
118.4(2)
118.8(2)
113.41(8)
111.44(8)
110.69(8)
104.28(9)
107.39(8)
109.28(9)
117.6(2)
117.7(2)
117.9(2)
Neq-M-CPh
C-Nax-C
a
b
Displacement of M atom from the plane defined by the three Neq atoms toward the Ph substituent. Displacement of Nax atom from
the plane defined by the three carbon atoms toward the metal atom.
F igu r e 1. Molecular structure of complex 5. Hydrogen
atoms are omitted for clarity. Displacement ellipsoids are
shown at the 50% probability level.
F igu r e 2. Molecular structure of complex 8. Hydrogen
atoms are omitted for clarity. Displacement ellipsoids are
shown at the 50% probability level.
trast to 5 and 8, the coordination polyhedron of the Ge
atom in compound 19 and the Sn atom in compound 10
represents a distorted trigonal bipyramid with N(1) (for
compound 19) or N(4) (for compound 10) and carbon
atoms C(11) (for 10) or C(1) (for 19) occupying the axial
positions and the three nitrogen atoms lying in equato-
rial sites. The Sn-CPh distances observed in two inde-
pendent molecules of 10 (2.172(2), 2.169(2) Å) are
comparable to those found for the related 1-phenylaza-
stannatrane N(CH2CH2NH)3Sn-C6H5, 2.155(3) and
2.177(3) Å.26 The SnrNax bonds (2.509(2) and 2.523(4)
Å) in 10 are much longer than those in the single X-ray
study of the azastannatrane N(CH2CH2NH)3Sn-C6H5,
2.380(2) and 2.453(2) Å.26 Similarly, the Ge-CPh bond
distance found in 19 (1.984(2) Å) is equal to that in 8,
and the GerNax distances in 19 (2.307(2) Å) are shorter
than that in 8.The Si-Neq bond distances in 5 (average
1.749 Å) are slightly longer than that in N(CH2CH2-
NH)3Si-C6H5 (average 1.739 Å).12 At the same time
Ge-Neq bond distances in 8 (average 1.856 Å) are
X-ray study of a quasi-azasilatrane, N(CH2CH2NSiMe3)3-
Si-Me (1) (2.775(7) Å).14 The formal substitution of the
Me3Si group by a hydrogen atom in compound 5 sharply
shortens the transannular SirNax distance (2.132(4) Å
for N(CH2CH2NH)3Si-C6H5).12The Si-C distance ob-
served in 5 (1.910(2) Å) is somewhat longer than that
in the closely related 1-phenylsilatrane N(CH2CH2O)3-
Si-C6H5 (1.882(6), 1.894(5), and 1.908(4) Å for different
crystal modifications)48-50 but slightly shorter than that
in 1-phenylazasilatrane N(CH2CH2NH)3Si-C6H5 (1.922-
(5) Å).12 Analogously, the Ge-C bond (1.985(2) Å) for
compound 8 is also longer than that in 1-phenylger-
matrane N(CH2CH2O)3Ge-C6H5 (1.947(6) Å).51In con-
(48) Turley, J . W.; Boer, F. P. J . Am. Chem. Soc. 1968, 90, 4026-
4030.
(49) Parkanyi, L.; Simon, K.; Nagy, J . Acta Crystallogr. 1974, B30,
2328-2332.
(50) Parkanyi, L.; Nagy, J .; Simon, K. J . Organomet. Chem. 1975,
101, 11-18.
(51) Lukevics, E.; Ignatovich, L.; Belyakov, S. J . Organomet. Chem.
1999, 588, 222-230.

520 Organometallics, Vol. 22, No. 3, 2003
Shutov et al.
In conclusion, metathetical exchange reactions be-
tween X-MCl3 (M ) Si, Ge, Sn) and lithiated parent
amines afforded compounds 1-12 in high yields. Tran-
samination reactions of X-M(NMe2)3 with Me-tren and
tren resulted in azagermatranes 19-25. The presence
of a transannular MrNax interaction in 10 and 19 was
proven by X-ray diffraction analysis; according to the
X-ray data, azametallatranes 5 and 8 possess extremely
weak transannular bonds.
Exp er im en ta l Section
Gen er a l Com m en ts. All solvents were dried by standard
methods and distilled before use. All reactions were carried
out under argon atmosphere using standard Schlenk tech-
niques. NMR spectra were recorded at 25 °C on Bruker AC
300 and Varian VXR 400 spectrometers; C6D6 was used as the
solvent and as internal deuterium lock in all cases except
1
where indicated. The chemical shifts in the H and 13C NMR
spectra are given in ppm relative to TMS. Elemental analyses
were carried out by the Microanalytical Laboratory of the
Chemistry Department of the Moscow State University and
by that of the Fachbereich Chemie of the Philipps-University
of Marburg (Heraeus-Rapid-Analyser). Mass spectra (EI-MS)
were recorded on a Varian CH-7a device using electron impact
ionization at 70 eV; mass spectra (FD-MS) were recorded on
a HP-5989B device; all assignments were made with reference
to the most abundant isotopes. X-MCl3 (M ) Si, Ge, Sn; R )
Me, Et, n-Bu, vinyl, and Ph) (Aldrich) were used as supplied.
Cl-Ge(NMe2)3,40 Me3-tren,52 and MeSi3-tren35 were prepared
according to the literature. C6D6 was obtained from Deutero
GmbH and dried over sodium/potassium alloy. The experi-
mental details of synthesis of 15-18 are given in the Sup-
porting Information.
F igu r e 3. Molecular structure of complex 10 (one inde-
pendent molecule). Hydrogen atoms are omitted for clarity.
Displacement ellipsoids are shown at the 50% probability
level.
Syn th esis of 1-P h en yl-N,N′,N′′-tr is(tr im eth ylsilyl)a za -
sila tr a n e, N(CH2CH2NSiMe3)3Si-P h (5). To a stirred solu-
tion of the tetraamine 13 (1.74 g, 4.8 mmol) in toluene (40 mL)
was added dropwise n-butyllithium (1.6 M in hexane, 6.1 mL,
9.8 mmol) at room temperature. The solution was stirred for
5 h. To this was added dropwise a solution of Ph-SiCl3 (0.69
g, 3.3 mmol) in toluene (10 mL) at room temperature with
stirring. The reaction mixture was stirred for a further 24 h,
and then all volatiles were removed under reduced pressure.
n-Pentane (20 mL) was added to the residue, and insoluble
substances were removed by filtration. The solution was
reduced in volume to one half and stored at -30 °C to obtain
colorless crystals of 5 (yield 0.82 g, 54%). 1H NMR (300.13
MHz): δ 0.13 (s, 27H, SiMe3), 2.40 (br s, 6H, NCH2), 2.82 (t,
6H, NCH2), 7.18-7.29 (m, 3H), 8.11-8.13 (m, 2H) Ph-
hydrogens. 13C NMR (75.47 MHz): δ 2.61 (SiMe3), 44.49 (N(Si)-
CH2), 58.21 (NCH2), 126.61, 127.75, 128.77, 137.46 (Ph-
carbons). 13C NMR (75.47 MHz, CDCl3): δ 2.32 (SiMe3), 44.14
(N(Si)CH2), 58.02 (NCH2), 126.03, 127.41, 128.99, 137.10 (Ph-
carbons). 29Si NMR (79.49 MHz): δ -22.02 (SiN3), 3.57 (SiMe3).
Anal. Calcd for C21H44N4Si4 (464.94): C, 54.25; H, 9.54; N,
12.05. Found: C, 41.90; H, 6.16; N, 7.95. EI-MS: 465 (7.2, M+),
450 (2.1, M+ - Me), 388 (5.8, M+ - Ph).
F igu r e 4. Molecular structure of complex 19. Hydrogen
atoms are omitted for clarity. Displacement ellipsoids are
shown at the 50% probability level.
shorter than that in 19 (average 1.877 Å). The formal
substitution of Me3Si groups by hydrogen atoms in 10
and N(CH2CH2NH)3Si-C6H5 does not influence signifi-
cantly the Sn-Neq bond distances (average for two
independent molecules: 2.058 and 2.058 Å, respec-
tively). The environment of the Nax atom in compounds
10 and 19 is approximately tetrahedral. For both
compounds, the axial nitrogen atoms are displaced by
0.38 Å from the plane defined by the three carbon atoms
toward the metal atom. In contrast, the deviations of
the Nax atom from the same planes in compounds 5 and
8 are significantly smaller (0.17 and 0.22 Å, respec-
tively).
A procedure similar to that for 5 was used for preparation
of 1-4 and 6-10.
1-Me t h yl-N ,N ′,N ′′-t r is(t r im e t h ylsilyl)a za sila t r a n e ,
N(CH2CH2NSiMe3)3Si-Me (1). Yield: 87%. 1H and 13C NMR
data are consistent with those already published.14
1-E t h y l-N ,N ′,N ′′-t r is (t r im e t h y ls ily l)a za s ila t r a n e ,
N(CH2CH2NSiMe3)3Si-Et (2). Yield: 83%. 1H NMR (300.13
MHz): δ 0.22 (s, 27H, SiMe3), 0.98 (q, 2H, SiCH2), 1.27 (t, 3H,
CH2CH3), 2.36 (br s, 6H, NCH2), 2.68 (t, 6H, NCH2). 13C NMR
(75.47 MHz): δ 1.94 (SiMe3), 10.63 (SiCH2), 14.95 (CH2CH3),
(52) Schmidt, H.; Lensink, C.; Xi, S. K.; Verkade, J . G. Z. Anorg.
Allg. Chem. 1989, 578, 75-80.

Azametallatranes of Group 14 Elements
Organometallics, Vol. 22, No. 3, 2003 521
44.45 (NCH2), 57.92 (NCH2). 29Si NMR (79.49 MHz): δ -21.44
(SiN3), 2.23 (SiMe3). Anal. Calcd for C17H44N4Si4 (416.90): C,
48.98; H, 10.64; N, 13.44. Found: C, 48.53; H, 10.25; N, 13.36.
tetraamine 14 (0.52 g, 2.8 mmol) in hexane (25 mL) was added
dropwise n-butyllithium (1.6 M in hexane, 5.25 mL, 8.4 mmol)
at room temperature. The mixture was stirred for 0.5 h. To
this was added dropwise a solution of vinyl-SiCl3 (0.45 g, 2.8
mmol) in toluene (10 mL) at room temperature with stirring.
The reaction mixture was stirred for a further 24 h, and all
volatiles were removed under reduced pressure. Toluene (20
mL) was added to the residue, and insoluble substances were
removed by filtration. All volatiles were removed in vacuo to
obtain 11 as a colorless oil (yield 0.18 g, 27%). 1H NMR (300.13
MHz): δ 2.22 (t, 6H, NCH2), 2.58 (t, 6H, NCH2), 2.67 (s, 9H,
CH3), 5.98-6.15 (m, 2H, dCH2), 6.39-6.52 (m, 1H, dC(Si)H).
13C NMR (75.47 MHz): δ 37.55 (Me), 49.75 (NCH2), 49.88
(NCH2), 129.20 (SiCHd), 141.73 (CH2d). Anal. Calcd for
EI-MS: 417 (0.5, M+), 402 (8.8, M+ - Me), 387 (100, M+
-
Et).
1-n -Bu t yl-N ,N ′,N ′′-t r is(t r im e t h ylsilyl)a za sila t r a n e ,
N(CH2CH2NSiMe3)3Si-n -Bu (3). Yield: 65%. 1H NMR (300.13
MHz): δ 0.25 (s, 27H, SiMe3), 0.97-1.77 (m, 9H, n-C4H9), 2.36
(br s, 6H, NCH2), 2.69 (t, 6H, NCH2). 13C NMR (75.47 MHz):
δ 1.99 (SiMe3), 14.07, 24.30, 27.87, 28.64 (CH2CH2CH2CH3),
44.47 (NCH2), 57.94 (NCH2). 29Si NMR (79.49 MHz): δ -21.47
(SiN3), 2.35 (SiMe3). Anal. Calcd for C19H48N4Si4 (444.95): C,
51.29; H, 10.87; N, 12.59. Found: C, 50.88; H, 10.53; N, 12.18.
EI-MS: 444 (0.1, M+), 429 (8.8, M+ - Me), 387 (100, M+
C4H9).
-
C
11H24N4Si (240.42): C, 54.95; H, 10.06; N, 23.30. Found: C,
55.31; H, 9.89; N, 23.47.
1-Vin y l-N ,N ′,N ′′-t r is (t r im e t h y ls ily l)a za s ila t r a n e ,
N(CH2CH2NSiMe3)3Si-Vin yl (4). Yield: 79%. 1H NMR
(300.13 MHz): δ 0.23 (s, 27H, SiMe3), 2.28 (br s, 6H, NCH2),
2.65 (t, 6H, NCH2), 5.91-6.03 (m, 2H, dCH2), 6.37-6.55 (m,
1H, dC(Si)H). 13C NMR (75.47 MHz): δ 2.41 (SiMe3), 43.23
(NCH2), 58.26 (NCH2), 131.05 (SiCHd), 144.80 (CH2d). 29Si
NMR (79.49 MHz): δ -24.71 (SiN3), 3.28 (SiMe3). Anal. Calcd
for C17H42N4Si4 (414.88): C, 49.21; H, 10.20; N, 13.50. Found:
C, 48.89; H, 9.95; N, 12.96. FD-MS: 414 (100, M+).
Syn th esis of 1-Meth yl-N,N′,N′′-tr im eth ylazager m atr an e,
N(CH2CH2NMe)3Ge-Me (12). A procedure similar to that
for 11 was used. Yield: 52%. 1H and 13C NMR data are
consistent with those already published.23
Syn th esis of 1-P h en yl-N,N′,N′′-tr im eth ylazager m atr an e,
N(CH2CH2NMe)3Ge-P h (19). A mixture of phenyltris(di-
methylamino)germane (15) (1.21 g, 4.3 mmol) and tetraamine
(14) (0.76 g, 4.04 mmol) was stirred at 130-135 °C for 2 h.
Evolution of dimethylamine was observed during heating. The
reaction mixture was allowed to cool to room temperature and
colorless liquid crystallized to a white solid. Crude product was
recrystallized from hot n-heptane to give 0.73 g (54%) of 19
as a white solid. 1H NMR (400.13 MHz): δ 2.26 (t, NCH2, 6H),
2.59 (s, NMe, 9H), 2.72 (t, NCH2, 6H), 7.20-7.35 (m, aromatic
protons), 8.08 (d, aromatic protons, 2H). 13C NMR (100.61
MHz): δ 39.74 (NMe), 50.38 (NCH2), 50.58 (NCH2), 122.01,
127.91, 136.34, 141.76 (aromatic carbons). Anal. Calcd for
1-Met h yl-N,N′,N′′-t r is(t r im et h ylsilyl)a za ger m a t r a n e,
N(CH2CH2NSiMe3)3Ge-Me (6). Yield: 44%. 1H NMR (300.13
MHz): δ 0.20 (s, 27H, SiMe3), 0.72 (s, 3H, GeMe), 2.23 (br s,
6H, NCH2), 2.68 (t, 6H, NCH2). 13C NMR (75.47 MHz): δ -3.07
(GeMe), 1.78 (SiMe3), 42.32 (NCH2), 58.75 (NCH2). Anal. Calcd
for C16H42GeN4Si3 (447.38): C, 42.96; H, 9.64; N, 12.52.
Found: C, 43.45.; H, 9.94.; N, 12.31. EI-MS: 433 (3.2, M+
-
Me), 408 (7.1, M+ - Me - Me3SiNCH2).
1-n -B u t y l-N ,N ′,N ′′-t r i s (t r i m e t h y ls i ly l)a z a g e r m a -
tr a n e, N(CH2CH2NSiMe3)3Ge-n -Bu (7). Yield: 71%. 1H
NMR (300.13 MHz): δ 0.24 (s, 27H, SiMe3), 0.96-1.84 (m, 9H,
n-C4H9), 2.31 (br s, 6H, NCH2), 2.72 (t, 6H, NCH2). 13C NMR
(75.47 MHz): δ 2.01 (SiMe3), 13.94, 27.29, 27.80, 28.42 (CH2-
CH2CH2CH3), 43.20 (NCH2), 59.13 (NCH2). Anal. Calcd for
C
15H26GeN4 (334.98): C, 53.78; H, 7.82; N, 16.73. Found: C,
54.30; H, 8.28; N, 17.32. EI-MS: 336 (1.5, M+), 280 (6.0, M+
-
CH2CH2NCH2), 259 (6.0, M+ - Ph).
A procedure similar to that for 19 was used for the
preparation of 20-24.
1-(1-N a p h t h y l)-N ,N ′,N ′′-t r im e t h y la za g e r m a t r a n e ,
N(CH2CH2NMe)3Ge-(1-n a p h th yl) (20). Yield: 53%. 1H
NMR (400.13 MHz): δ 2.29 (t, NCH2, 6H), 2.49 (s, NMe, 9H),
C
19H48GeN4Si3 (489.46): C, 46.62; H, 9.88; N, 11.45. Found:
C, 46.08; H, 9.74; N, 11.12. EI-MS: 491 (4.5, M+), 476 (12.3,
M+ - Me), 433 (100, M+ - C4H9), 389 (54.1, M+ - Me3SiNCH2).
1-P h en yl-N,N′,N′′-t r is(t r im et h ylsilyl)a za ger m a t r a n e,
N(CH2CH2NSiMe3)3Ge-P h (8). Yield: 49%. 1H NMR (300.13
MHz): δ 0.15 (s, 27H, SiMe3), 2.34 (br s, 6H, N(Si)CH2), 2.83
(t, 6H, NCH2), 7.16-7.27 (m, 3H), 8.10-8.13 (m, 2H) Ph-
hydrogens. 13C NMR (75.47 MHz): δ 2.59 (SiMe3), 43.28 (N(Si)-
CH2), 59.31 (NCH2), 127.23, 128.35, 129.03, 136.19 (Ph-
carbons). Anal. Calcd for C21H44GeN4Si3 (509.45): C, 49.51;
H, 8.71; N, 11.00. Found: C, 49.30; H, 8.64; N, 10.46. EI-MS:
510 (2.1, M+), 450 (7.7, M+ - Me), 433 (2.3, M+ - Ph), 408
(95.5, M+ - Me3SiNCH2).
2.76 (t, NCH
2, 6H), 7.29-7.51 (m, aromatic protons), 7.72-
7.75 (m, aromatic protons), 8.59 (d, aromatic proton, 1H), 8.81
(d, aromatic proton, 1H).
13C NMR (100.61 MHz): δ 39.67
(NMe), 50.35 (NCH
2), 50.64 (NCH2), 125.34, 125.78, 125.88,
128.88, 129.23, 130.81, 134.21, 134.98, 138.68, 140.76 (aro-
matic carbons). Anal. Calcd for C
19H28GeN4 (385.04): C, 59.26;
H, 7.33; N, 14.55. Found: C, 59.16; H, 7.35; N, 14.13. EI-MS:
386 (4.5, M+
- C10H7).
), 330 (23.0, M+ - CH2CH2NCH2), 259 (24.3, M+
1-(9-An t h r a cen yl)-N,N′,N′′-t r im et h yla za ger m a t r a n e,
N(CH 2CH2NMe)3Ge-(9-a n tr a cen yl) (21). Yield: 34%. 1H
NMR (400.13 MHz): δ 2.29 (t, NCH2, 6H), 2.37 (s, NMe, 9H),
2.82 (t, NCH2, 6H), 7.23 (d, aromatic protons, 2H), 7.32-7.36
(m, aromatic protons), 7.52-7.55 (m, aromatic protons), 7.90
(d, aromatic protons, 2H), 8.32 (s, aromatic proton, 1H). 13C
NMR (100.61 MHz): δ 39.55 (NMe), 50.56 (NCH2), 50.80
(NCH2), 124.89, 125.09, 129.21, 129.38, 131.03, 132.19, 138.48,
1-n -B u t y l-N ,N ′,N ′′-t r is (t r im e t h y ls ily l)a za s t a n n a -
tr a n e, N(CH2CH2NSiMe3)3Sn -n -Bu (9). Yield: 61%. 1H
NMR (300.13 MHz): δ 0.24 (s, 27H, SiMe3), 0.94-1.63 (m, 9H,
n-C4H9), 2.06 (t, 6H, NCH2), 2.77 (t, 6H, NCH2). 13C NMR
(75.47 MHz): δ 2.19 (SiMe3), 13.88, 26.51, 28.27, 29.14 (CH2-
CH2CH2CH3), 41.45 (NCH2), 60.58 (NCH2). Anal. Calcd for
C
19H48N4Si3Sn (435.56): C, 42.61; H, 9.03; N, 10.46. Found:
C, 42.29; H, 8.78; N, 10.22. EI-MS: 322 (7.1, M+ - C4H9
Me3SiN - Me3Si).
-
139.89 (aromatic carbons). Anal. Calc. for
C23H30GeN4
(435.10): C, 63.49; H, 6.95; N, 12.88. Found: C, 63.70; H, 6.88;
N, 12.54. EI-MS: 436 (5.5, M+), 379 (10.7, M+ - CH2CH2NMe),
259 (11.0, M+ - C14H9).
1-P h e n y l-N ,N ′,N ′′-t r is (t r im e t h y ls ily l)a z a s t a n n a -
tr a n e, N(CH2CH2NSiMe3)3Sn -P h (10). Yield: 47%. 1H
NMR (300.13 MHz): δ 0.17 (s, 27H, SiMe3), 2.10 (t, 6H, NCH2),
2.85 (t, 6H, NCH2), 7.24-7.32 (m, 3H), 8.10-8.11 (m, 2H) Ph-
hydrogens. 13C NMR (75.47 MHz): δ 1.33 (SiMe3), 42.75 (N(Si)-
CH2), 60.73 (NCH2), 126.12, 127.45, 128.83, 134.90 (Ph-
carbons). Anal. Calcd for C21H44N4Si3Sn (555.55): C, 45.40; H,
7.98; N, 10.08. Found: C, 45.11; H, 8.30; N, 10.21. EI-MS: 147
(100).
1-(9-P h e n a n t h r e n y l)-N ,N ′,N ′′-t r im e t h y la za g e r m a -
tr a n e, N(CH2CH2NMe)3Ge-(9-p h en a n tr en yl) (22). Yield:
23% ((NH4)2SO4, 10 mol %, was added to the reaction mixture).
1H NMR (400.13 MHz): δ 2.28 (t, NCH2, 6H), 2.53 (s, NMe,
9H), 2.77 (t, NCH2, 6H), 7.36-7.59 (m, aromatic protons) 7.90
(d, aromatic proton, 1H), 8.54 (d, aromatic proton, 1H), 8.60
(d, aromatic proton, 1H), 8.90 (s, aromatic proton, 1H). 13C
NMR (100.61 MHz): δ 39.76 (NMe), 50.32 (NCH2), 50.67
(NCH2), 122.86, 123.01, 123.13, 126.09, 126.59, 126.83, 129.34,
Syn th esis of 1-Vin yl-N,N′,N′′-tr im eth yla za sila tr a n e,
N(CH2CH2NMe)3Si-Vin yl (11). To a stirred solution of the

522 Organometallics, Vol. 22, No. 3, 2003
Shutov et al.
130.66, 131.43, 131.52, 132.54, 136.77, 136.82, 139.39 (aro-
matic carbons). Anal. Calcd for C23H30GeN4 (435.10): C, 63.49;
H, 6.95; N, 12.88. Found: C, 63.54; H, 7.23; N, 12.48. EI-MS:
436 (3.6, M+), 259 (7.9, M+ - C14H9).
131.29, 131.67, 132.05, 134.75, 136.18, 143.14 (aromatic
carbons). Anal. Calcd for C20H24GeN4 (393.02): C, 61.12; H,
6.15; N, 14.25. Found: C, 60.81; H, 6.23; N, 14.39. EI-MS: 217
(1.3, M+ - C10H7).
1-P h en yla za ger m a tr a n e, N(CH 2CH2NH)3Ge-P h (23).
Sylila tion Rea ction of 1-P h en yla za ger m a tr a n e (24). To
a stirred solution of 24 (0.30 g, 1.0 mmol) in THF (15 mL) was
added dropwise n-butyllithium (1.6 M in hexane, 2.00 mL, 3.2
mmol) at -78 °C. The mixture was stirred for 10 min at this
temperature and an additional 4 h at room temperature. To
this was added dropwise a solution of Me3SiCl (0.45 mL, 3.7
mmol) in THF (5 mL) at -40 °C with stirring. The reaction
mixture was stirred for a further 12 h at room temperature,
and all volatiles were removed under reduced pressure.
n-Hexane (20 mL) was added to the residue, and insoluble
substances were removed by filtration. All volatiles were
removed in vacuo to obtain a yellow oil, containing according
to 1H NMR spectroscopy data a minor quantity of azager-
matrane 8.
X-r a y Cr ysta llogr a p h y. Table 2 summarizes crystal data
as well as details of the data collection and structure refine-
ment for compounds 5, 8, 10, and 19. All presented structures
were solved by direct methods43 and refined by full matrix
least-squares on F2 with anisotropic thermal parameters for
all non-hydrogen atoms.44 In the structures of 5, 8, and 10
hydrogen atoms were placed in calculated positions and refined
using a riding model. As for 19, all hydrogen atoms were
refined isotropically.
1
Yield: 79%. H NMR (400.13 MHz): δ 0.68 (br s, GeNH, 3H),
2.20 (t, NCH2, 6H), 2.78 (t, NCH2, 6H), 7.21-7.28 (m, aromatic
protons, 3H), 7.79 (d, aromatic protons, 2H). 13C NMR (100.61
MHz): δ 38.47 (NCH2), 52.53 (NCH2), 127.94, 128.33, 133.51,
146.87 (aromatic carbons). Anal. Calcd for
C12H20GeN4
(292.90): C, 49.21; H, 6.88; N, 19.13. Found: C, 49.47; H, 6.81;
N, 19.29. EI-MS: 292 (2.0, M+), 277 (5.5, M+ - CH3), 217 (9.6,
M+ - Ph).
1-(1-Na p h th yl)a za ger m a tr a n e, N(CH2CH2NH)3Ge-(1-
1
n a p h th yl) (24). Yield: 65%. H NMR (400.13 MHz): δ 0.82
(s, GeNH, 3H), 2.30 (t, NCH2, 6H), 2.85 (t, NCH2, 6H), 7.39-
7.55 (m, aromatic protons, 3H), 7.82 (t, aromatic protons, 2H),
8.24 (d, aromatic proton, 1H), 9.17 (d, aromatic proton, 1H).
13C NMR (100.61 MHz): δ 38.86 (NCH2), 53.55 (NCH2), 121.73,
125.34, 128.93, 129.05, 131.03, 132.82, 134.63, 137.91, 144.90
(aromatic carbons, one crossed with C6D6 signals). Anal. Calcd
for C16H22GeN4 (342.96): C, 56.03; H, 6.47; N, 16.34. Found:
C, 55.85; H, 6.13; N, 16.56. EI-MS: 344 (4.5, M+), 217 (13.0,
M+ - C10H7).
Syn t h esis of 1-(9-P h en a n t h r en yl)a za ger m a t r a n e, N-
(CH2CH2NMe)3Ge-(9-p h en a n tr en yl) (25). A mixture of
9-phenanthrenylnyltris(dimethylamino)germane (2.62 g, 6.8
mmol) and tren (0.95 g, 6.5 mmol) was stirred and heated at
170-180 °C for 11 h. Slow evolution of dimethylamine was
observed. The reaction mixture was allowed to cool to room
temperature, and brown oil crystallized to solid. The reaction
mixture was treated with toluene (25 mL), and insoluble
residue were filtered off. Toluene was removed in vacuo, and
residue was recrystallized from hot n-heptane. 25 was obtained
as a yellow solid in 22% yield (0.57 g). 1H NMR (400.13 MHz):
δ 0.73 (s, GeNH, 3H), 2.19 (t, NCH2, 6H), 2.76 (t, NCH2, 6H),
7.38-7.58 (m, aromatic protons, 4H), 7.84 (d, aromatic proton,
1H), 8.54 (d, aromatic proton, 1H), 8.55 (s, aromatic proton,
1H), 8.62 (d, aromatic proton, 1H), 9.14 (d, aromatic proton,
1H). 13C NMR (100.61 MHz): δ 38.94 (NCH2), 53.67 (NCH2),
122.81, 123.27, 126.03, 126.21, 126.65, 126.73, 129.14, 131.11,
Ack n ow led gm en t. This work was supported by the
Russian Foundation for Basic Research under Grant No.
01-03-32474 for A.V.C. and INTAS under Grant No.
YSF 2001/2-135 for S.S.K. as well as from the Philipps-
University Marburg, Chemistry Department, for P.L.S.
Su p p or tin g In for m a tion Ava ila ble: X-ray crystallo-
graphic files, in CIF format, for the structures of 5, 8, 10, and
19 as well as experimental details of the syntheses of 15-18.
This material is available free of charge via the Internet at
http://pubs.acs.org.
OM020708H