Penta-coordinated chlorosilanes: Reaction chemistry, structure and bonding

Article abstract of DOI:10.1016/S0022-328X(98)00554-3

The synthesis and reaction behavior of the penta-coordinated chlorosilanes [C₆H₄CH₂N(CH₃) ₂-2]Si(Cl)(R)(R′) [3a: R = R′ = Cl; 3b: R = R′ = CH₃; 3c: R = Cl, R′= CH₃; 3d: R = Cl, R′ = CH=CH₂; 3e: R = CH₃, R′ = CH=CH₂] are discussed. Compounds 3a-e can be obtained by the reaction of LiC₆H₄CH₂N(CH₃)₂-2 (1) with stoichiometric amounts of (R)(R′)SiCl₂ (2) in high yields and give access to a versatile reaction chemistry on substitution of the chlorine atoms by many of the diverse nucleophiles used. Hydrolysis of compound 3d produces oligomeric {[C₆H₄CH₂N(CH₃) ₂-2](CH2=CH)SiO}_n (4a), whereas 3e yields the disiloxane {[C₆H₄CH₂N(CH₃) ₂-2](CH₂=CH)(CH₃)Si}₂O (4b). Alcoholysis of compounds 3d and 3e in presence of NEt₃ affords [C₆H₄CH₂N(CH₃) ₂-2](CH₂=CH)(CH₃)Si(OCH₃) (5a) or [C₆H₄CH₂N(CH₃) ₂-2](CH₂=CH)Si(OR)₂ [5b: R = CH₃, 5c: R = C₂H₅, 5d: R = ⁱC₃H₇], respectively. Compound 5b can be transferred to the difluorosilane derivative [C₆H₄CH₂N(CH₃) ₂-2](CH₂=CH)SiF₂ (6) by its reaction with BF*₃O(C₂H₅)₂, while treatment with LiAlH₄ produces the silane [C₆H₄CH₂N(CH₃) ₂-2](CH2=CH)SiH₂ (7a). Moreover, hypervalent silanes are accessible by the reaction of chloro-functionalized 3d or 3e with LiAlH₄ whereby compounds [C₆H₄CH₂N(CH₃)](H ₂C=CH)Si(H)(R) (7a: R = H; 7b: R = CH₃) are formed in good yields. Metathesis reaction of compounds 3b-e with LiR reagents [R = C=CR′, NHC₆H₂(CH₃)₃-2,4,6, P(C₆H₅)2] produces [C₆H₄CH₂N(CH₃) ₂-2](CH₃)(R)(SiC=CR′) [reaction of 3b or 3e with LiC=CR′; 8a: R = CH₃, R′ = C₆H₅; 8b: R = CH₃, R′ = Si(CH₃)₃; 8c: R = CH=CH₂, R′ = C₆H₅; 8d: R = CH=CH2, R′ = Si(CH₃)₃], [C₆H₄CH₂N(CH₃) ₂-2](R)Si(C=CR′)₂ [reaction of 3c or 3d with LiC=CR′; 9a: R = CH₃, R′ = C₆H₅; 9b: R = CH=CH₂, R′ = C₆H₅; 9c: R = CH=CH₂, R = Si(CH₃)₃], [C₆H₄CH₂N(CH₃) ₂-2](H2C=CH)Si[HNC6H2(CH₃)₃-2,4,6]₂ [reaction of 3d with LiNHC₆H₂(CH₃)₃-2,4,6; 10] or [C₆H₄CH₂N(CH₃)₂-2](H ₂C=CH)Si[P(C₆H₅)₂]₂ [reaction of 3d with LiP(C₆H₅)₂; 11]. The solid state structures of 3c and 3d are reported. Complex 3c crystallizes in the monoclinic space group P2₁ with a = 8.918(5), b= 11.557(3), c= 12.830(7) A; β= 108.17(4)°, V = 1256(5) A³ and Z = 4; 3d crystallizes in the monoclinic space group P2₁ with a = 6.625(3), b = 8.574(6), c = 11.281(8) A; β= 88.16(5)°, V = 640.5(7) A³ and Z = 2. The central silicon atom in compounds 3c and 3d shows an essentially distorted trigonal-bipyramidal coordination sphere, with the axial positions occupied by the nitrogen donor atom and one chloro ligand. Dynamic ¹H-NMR studies confirm that the same geometry is adopted in solution.

Full text of DOI:10.1016/S0022-328X(98)00554-3

Journal of Organometallic Chemistry 563 (1998) 61–72
Penta-coordinated chlorosilanes: reaction chemistry, structure and
bonding
Markus Weinmann b, Anja Gehrig a, Berthold Schiemenz c, Gottfried Huttner c,
Bernhard Nuber c, Gerd Rheinwald a, Heinrich Lang a,*
a Technische Uni6ersita¨t Chemnitz, Institut fu¨r Chemie, Lehrstuhl Anorganische Chemie, Straße der Nationen 62, D-09111 Chemnitz, Germany
b Max-Planck-Institut fu¨r Metallforschung, Institut fu¨r Werkstoffwissenschaften, Heisenbergstraße 5, D-70569 Stuttgart, Germany
c Uni6ersita¨t Heidelberg, Anorganisch-Chemisches Institut, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany
Received 16 December 1997; received in revised form 5 February 1998
Abstract
The synthesis and reaction behavior of the penta-coordinated chlorosilanes [C6H4CH2N(CH3)2-2]Si(Cl)(R)(R%) [3a: R=R%=Cl;
3b: R=R%=CH3; 3c: R=C1, R%=CH3; 3d: R=Cl, R%=CHꢀCH2; 3e: R=CH3, R%=CHꢀCH2] are discussed. Compounds
3a–e can be obtained by the reaction of LiC6H4CH2N(CH3)2-2 (1) with stoichiometric amounts of (R)(R%)SiCl2 (2) in high yields
and give access to a versatile reaction chemistry on substitution of the chlorine atoms by many of the diverse nucleophiles used.
Hydrolysis of compound 3d produces oligomeric {[C6H4CH2N(CH3)2-2](CH2ꢀCH)SiO}n (4a), whereas 3e yields the disiloxane
{[C6H4CH2N(CH3)2-2](CH2ꢀCH)(CH3)Si}2O (4b). Alcoholysis of compounds 3d and 3e in presence of NEt3 affords
[C6H4CH2N(CH3)2-2](CH2ꢀCH)(CH3)Si(OCH3) (5a) or [C6H4CH2N(CH3)2-2](CH2ꢀCH)Si(OR)2 [5b: R=CH3, 5c: R=C2H5, 5d:
R=iC3H7], respectively. Compound 5b can be transferred to the difluorosilane derivative [C6H4CH2N(CH3)2-2](CH2ꢀCH)SiF2 (6)
by its reaction with BF*3 O(C2H5)2, while treatment with LiAlH4 produces the silane [C6H4CH2N(CH3)2-2](CH2ꢀCH)SiH2 (7a).
Moreover, hypervalent silanes are accessible by the reaction of chloro-functionalized 3d or 3e with LiAlH4 whereby compounds
[C6H4CH2N(CH3)2](H2CꢀCH)Si(H)(R) (7a: R=H; 7b: R=CH3) are formed in good yields. Metathesis reaction of compounds
3b–e with LiR reagents [R=CꢁCR%, NHC6H2(CH3)3-2,4,6, P(C6H5)2] produces [C6H4CH2N(CH3)2-2](CH3)(R)(SiCꢁCR%) [reac-
tion of 3b or 3e with LiCꢁCR%; 8a: R=CH3, R%=C6H5; 8b: R=CH3, R%=Si(CH3)3; 8c: R=CHꢀCH2, R%=C6H5; 8d:
R=CHꢀCH2, R%=Si(CH3)3], [C6H4CH2N(CH3)2-2](R)Si(CꢁCR%)2 [reaction of 3c or 3d with LiCꢁCR%; 9a: R=CH3, R%=C6H5;
9b: R=CHꢀCH2, R%=C6H5; 9c: R=CHꢀCH2, R=Si(CH3)3], [C6H4CH2N(CH3)2-2](H2CꢀCH)Si[HNC6H2(CH3)3-2,4,6]2 [reac-
tion of 3d with LiNHC6H2(CH3)3-2,4,6; 10] or [C6H4CH2N(CH3)2-2](H2CꢀCH)Si[P(C6H5)2]2 [reaction of 3d with LiP(C6H5)2; 11].
The solid state structures of 3c and 3d are reported. Complex 3c crystallizes in the monoclinic space group P21/c with a=8.918(5),
3
˚
˚
b=11.557(3), c=12.830(7) A; i=108.17(4)°, V=1256(5) A and Z=4; 3d crystallizes in the monoclinic space group P21 with
3
˚
˚
a=6.625(3), b=8.574(6), c=11.281(8) A; i=88.16(5)°, V=640.5(7) A and Z=2. The central silicon atom in compounds 3c
and 3d shows an essentially distorted trigonal-bipyramidal coordination sphere, with the axial positions occupied by the nitrogen
donor atom and one chloro ligand. Dynamic H-NMR studies confirm that the same geometry is adopted in solution. © 1998
1
Elsevier Science S.A. All rights reserved.
Keywords: Penta-coordination; Chlorosilanes; Synthesis, Reaction behavior
1. Introduction
Recently, there has been a wide interest in hyperva-
lent silicon species [1], as these compounds have been
proposed as intermediates or transition states in many
* Corresponding author. Fax: +49 371 5311833; e-mail: hein-
rich.lang@chemie.tu-chemnitz.de
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00554-3

62
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
Compounds 3a–e were the only products, which
could be isolated by extraction of the reaction residues
with dichloromethane, followed by filtration through a
pad of Celite. While compounds 3a–d could be crystal-
chemical reactions ([1]a,b,f). Auner, Corriu as well as
Zybill have shown that hypervalent silicon species of
type [C6H4CH2N(CH3)2-2](R)SiCl2 or [C6H4CH2N
(CH3)2-2](R)SiH2 are well suited for the synthesis and
stabilization of low-valent silanediyl transition metal
compounds of type [C6H4CH2N(CH3)2-2](R)SiꢀMLn
(MLn=Fe(CO)4, Cr(CO)5, (p5-C5H5)Mn(CO)2; R=H,
aryl) [2].
In the course of our studies, concerning the synthesis
and reaction chemistry of heterobutadiene and het-
eroallyl y-systems, containing main group elements as
well as transition metal atoms [3–5], we were interested
in using penta-coordinated silicon compounds, which
additionally feature organic y-systems such as vinyl or
alkynyl groups in order to synthesize highly unsatu-
rated compounds of type [C6H4CH2N(CH3)2-
2](R)SiꢀMLn (MLn=16-valence electron transition
metal fragment, R=organic y-system). In these
silanediyl complexes, next to an silicon–metal double
bond unit an organic y-system is located. This arrange-
ment allows an direct internal comparison of the reac-
tion behavior of both an organometallic and organic
y-system next to each other.
lized
as
colorless
solids
from
saturated
dichloromethane/n-pentane solutions upon cooling to
−30°C, compound 3e was obtained as an oil, which
could be further purified by vacuum distillation. All
compounds synthesized are soluble in most polar or-
ganic solvents and decompose rapidly on exposition to
air.
Compounds 3a–e were spectroscopically character-
1
ized by dynamic H-NMR and temperature dependent
29Si{1H}-NMR studies ([1]a, [9]). All these compounds
contain a CH2NMe2 built-in arm, resulting in an penta-
coordinated environment around the silicon atom.
While hypervalent silicon molecules of the latter type
are well studied in solution, only little is known about
their solid state structure [8,10].
The X-ray structures of penta-coordinated 3c and 3d
were determined in order to clearly confirm the in-
tramolecular N–Si coordination of compounds 3a–e in
the solid state. The result of the X-ray structure analy-
sis is shown in Fig. 1. Crystallographic parameters for
compounds 3c and 3d are listed in Table 1, selected
bond lengths and angles are given in Table 2 and
atomic coordinates as well as anisotropic thermal
parameters are depicted in Tables 3 and 4.
In this context, we here report the synthesis and the
reaction chemistry of hypervalent chlorofunctionalized
silanes, to gain further information on nucleophilic
substitution reactions at five-coordinated silicon atoms.
Compounds 3c and 3d crystallize in the monoclinic
space group P21/c (3c) and P21 (3d). Both compounds
are characterized by a slightly distorted trigonal-bipyra-
midal coordinated silicon atom. The nitrogen atom N1
of the C6H4CH2N(CH3)2 ligand is dative bonded to the
silicon center and occupies an apical position of the
trigonal bipyramid. Additionally, in both structures a
chlorine atom (Cl1) is found in the apical position: This
atom and the dative bonded nitrogen atom N1 are
facing each other. This is in agreement with the in-
creased ease of stretching the Cl–Si bond in compari-
son with the Si–C bonds of the methyl or vinyl groups
present in compounds 3c or 3d. The N–Si distances of
2. Results and discussion
2.1. Synthesis
The penta-coordinated chlorosilanes [C6H4CH2N
(CH3)2-2](Cl)Si(R)(R%) (3a: R=R%=Cl; 3b: R=R%=
CH3; 3c: R=Cl, R%=CH3; 3d: R=Cl, R%=CHꢀCH2;
3e: R=CH3, R%=CHꢀCH2) were prepared by reacting
equimolar amounts of LiC6H4CH2N(CH3)2-2 (1) [6]
with the appropriate chlorosilanes (R)(R%)SiCl2 (2) in
diethyl ether solutions at ambient temperature, accord-
ing to methods firstly described by van Koten [7] and
Corriu et al. [1,8].
˚
2.183(3) and 2.257(7) A in 3c and 3d, respectively, are
relatively short, indicating a substantial bonding inter-

M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
63
Table 1
action
as
compared
with
isostructural
Crystallographic parameters for compounds 3c and 3d
[C6H4CH2N(CH3)2-2](CH3)SiF2 ([10]e). The shorter
Si1–N1 bond in 3c in contrast to the corresponding
Si1–N1 bond in compound 3d is reflected in a longer
3c
3d
Formula
FW
C10H15Cl2NSi
248.21
Monoclinic
P21/c
8.918(5)
11.557(3)
12.830(7)
108.17(4)
1256.4(10)
1.31
C11H15Cl2NSi
260.23
Monoclinic
P21
6.625(3)
8.574(6)
11.281(8)
88.16(5)
640.5(7)
1.35
˚
˚
Si–Cl1 bond in 3c (2.233(1) A) than in 3d (2.194(3) A)
(Table 2). In both compounds the N1–Si1–Cl1 axis are
essentially linear [3c 176.3(1), 3d 175.0(2)°] (Table 2).
The vinyl group in 3d is not in-plane bonded with the
atoms C1, C10, Cl2 and Si1 [interplanar angle C1, C10,
Cl2, Si1/Si1, C10, C11: 54.9(5)°]. An internal compari-
son of the Si–C1 bond distances Siax–Cl and Sieq–C1
in compounds 3c [Si1–Cl1 2.233(1), Si1–Cl2 2.087(2)
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
i (°)
3
˚
V (A )
Dcalc. (g cm−3
)
Z
4
2
˚
˚
A] and 3d [Si1–Cl1 2.194(3), Si1–Cl2 2.081(3) A]
(Table 2) shows that in each case the Siax–Cl distances
are significantly elongated as compared with the appro-
priate Sieq–Cl bond lengths ([1]a,d, [10]). The Si–C
separations found in compounds 3c and 3d are in the
range of values usually found for tetravalent derivatives
[11].
Crystal size (mm3)
0.30×0.25
0.25×0.30×0.50
×0.25
Diffraction model
Siemens R3m/ Siemens R3m/V
V
0.58
v (mm−1
Radiation (u, A)
)
0.57
˚
Mo–Kh
(0.71073)
293
ꢀ-Scan
0.75
2.3–29.3
3.0–51.0
−105h510,
Mo–Kh (0.71073)
T (K)
Scan mode
Scan range Dꢀ (°)
Scan speed (° min−1
2q range (°)
272
ꢀ-Scan
0.75
2.3–29.3
3.6–48
−45h57, −95k5
The structures of molecules 3a–e adopted in the solid
state could also be confirmed in solution by tempera-
)
Index ranges
05k514, 05 9, −125l512
l515
Unique reflections
Observed [I]2|(I)]
Refined parameters
2340
1431
130
1069
1026
143
Largest difference peak
0.234/−0.279
0.675/−0.650
−3
˚
and hole (e A
)
R1/wRa2 [I\2|(I)]
0.0462/0.1134
0.0957/0.1281
0.0559/0.1522
0.0595/0.1533
0.980
R1/wRa2 (all)
S (goodness-of-fit)b on F2 1.174
a R1=S(ꢀFoꢁ−ꢁFcꢀ)/SꢁFoꢁ], wR2=S(w(F2o−F2c)2)/S(wFo4)]0.5
.
b S=Sw(Fo2−Fc2)2]/(n−p)0.5; n, number of reflections; p, parameters
used.
Definition of w (where P=(F2o+2Fc2)/3]:
3c: w=1/[|2(F2o)+(0.0716P)2+0.0000P]
3d: w=1/[|2(F2o)+(0.1121P)2+0.4098P].
1
ture dependent H-NMR (3b–e) or 29Si{1H}-NMR ex-
periments (3a–e) (Sections 2.3 and 3) [12].
2.2. Reaction beha6ior
The intramolecular N–Si coordination found for all
compounds 3a–e is accompanied by an enhanced reac-
tivity of these compounds when compared with tetrava-
lent silicon species [1,2]. For example, hydrolysis of
molecules 3d or 3e produces without added catalyst at
low
{[C6H4CH2N(CH3)2-2](H2CꢀCH)SiO}n (4a) or the dis-
iloxane {[C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)Si}2O
(4b) at 25°C in THF.
temperature
the
polymeric
siloxane
Fig. 1. ZORTEP drawings (drawn at 50% probability level) of
compounds 3c (top) and 3d (bottom) with the atom numbering
schemes.

64
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
While hydrolysis of compounds 3d and 3e is straight-
forward, the reaction of these compounds with less
acidic alcohols requires the presence of a Lewis base,
such as triethylamine. The chlorosilanes 3d and 3e were
therefore refluxed with N(C2H5)3 in alcoholic solutions
A further possibility for the preparation of five-coor-
dinated vinylated silanes is given by the reaction of
[C6H4CH2N(CH3)2-2](H2CꢀCH)(R)SiCl (3d: R=C1,
3e: R=CH3) with LiAlH4 in diethyl ether at 25°C. The
silanes [C6H4CH2N(CH3)2-2](CH2ꢀCH)(R)SiH [7a:
R=H, 7b: R=CH3] are formed in 57 or 54% yield,
respectively.
i
(CH3OH, C2H5OH, C3H7OH), causing the precipita-
tion of N(C2H5)3 ·HC1. The mono- (5a) or disubsti-
tuted silylethers (5b–d) are obtained as colorless oils in
yields between 48–65% after appropriate work-up.
Likewise, the chloro atoms in compounds 3b–e can
be replaced by different organic entities, e.g. alkynyls,
amines and phosphines.
The mono- and di-alkynyl substituted silanes
[C6H4CH2N(CH3)2-2](CH3)(R)Si(CꢁCR%) [8a: R=CH3,
R%=C6H5; 8b: R=CH3, R%=Si(CH3)3; 8c: R=
CHꢀCH2, R%=C6H5; 8d: R=CHꢀCH2, R%=Si(CH3)3]
and [C6H4CH2N(CH3)2-2](R)Si(CꢁCR%)2 [9a: R=CH3,
R%=C6H5; 9b: R=CHꢀCH2, R%=C6H5; 9c: R=
CHꢀCH2, R%=Si(CH3)3] can be synthesized by reacting
equimolar amounts of the chlorosilane starting materi-
als 3b–e with LiCꢁCR% in diethlyl ether solutions at
ambient temperature. Depending on the nature of the
organic ligands R and R%, compounds 8 and 9 can be
obtained in 50–85% yield.
Compound 5b can successfully be used as a starting
material for the synthesis of the hypervalent difluorosi-
lane 6 or the silane 7a by treatment with (C2H5)2O·BF3
in n-pentane or with LiAlH4 in diethyl ether solutions
at 25°C.

M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
65
2.3. Spectroscopic studies
The new synthesized compounds represent colorless
oils (3e and 4–7) or solids (3a–d and 8–11: colorless;
10: orange; 11: off-white). While compounds 4–9 are
soluble in most common organic solvents, molecules 3,
10 and 11 can only be dissolved in polar solvents, such
as dichloromethane, THF or acetone. Compounds 5–7,
as well as 10 and 11, can be handled in air only for very
short periods of time, whereas the oligosiloxane 4a, the
disiloxane 4b and the alkynyl functionalized silanes 8
and 9 are stable to air.
Compounds 3–11 were completely characterized by
1
elemental analysis and spectroscopic studies (IR, H-,
13C{1H}-, 29Si{1H}-, 31P{1H}-NMR, MS).
The utilization of IR spectroscopy represents a reli-
able method for the rapid identification of the different
functional ligands present in compounds 3–11. IR spec-
tra show the characteristic frequencies in the expected
region of the functionalized groups, e.g. Si–O, Si–H,
N–H, CꢀC and CꢁC. The most remarkable feature in
compounds [C6H4CH2N(CH3)2-2](H2CꢀCH)(R)SiH [7a:
R=H; 7b: R=CH3] is the observation of two Si–H
stretching vibrations Si–Heq and Si–Hax at 2135 (vs)
and 2081 (m) cm−1 in 7a or 2133 (vs) and 2094 (m)
cm−1 in 7b. This is of major importance to clearly
determine the structure of the hypervalent hydridosi-
lanes 7a and 7b. It points out that at least different
An access to amino- or phosphino-functionalized
penta-coordinated silicon compounds is given by the
reaction of the hypervalent dichlorosilane 3d with two
equivalents of LiNHMes (Mes=C6H2(CH3)3-2,4,6;
synthesis of compound 10) or LiP(C6H5)2 (synthesis of
compound 11).
Table 2
a
˚
Selected bond lengths (A) and angles (°) for compounds 3c and 3d
3c
3d
˚
Bond lengths (A)
Si1–N1
Si1–C11
Si1–Cl2
Si1–C2
Si1–C8
N1–C1
N1–C9
N1–C10
2.183(3)
2.233(1)
2.087(2)
1.863(3)
1.873(3)
1.492(4)
1.488(4)
1.484(4)
Si1–N1
Si1–Cl1
Si1–Cl2
Si1–C10
Si1–C1
N1–C7
N1–C8
N1–C9
2.257(7)
2.194(3)
2.081(3)
1.850(7)
1.880(7)
1.461(10)
1.490(10)
1.498(10)
Bond angles (°)
Cl1–Si1–Cl2
N1–Si1–Cl1
N1–Si1–Cl2
C2–Si1–Cl2
C8–Si1–Cl2
C2–Si1–C8
Si1–N1–C1
S1–N1–C9
Si1–N1–C10
C1–N1–C9
C1–N1–C10
C9–N1–C10
92.9(1)
176.3(1)
88.6(1)
Cl1–Si1–Cl2
N1–Si1–Cl1
N1–Si1–Cl2
C1–Si1–C12
C10–Si1–C12
C1–Si1–C10
C7–N1–C8
C7–N1–C9
C7–N1–Si1
C8–N1–C9
C8–N1–Si1
C9–N1–Si1
Si1–C10–C11
93.4(1)
175.0(2)
86.7(2)
Compounds 8–11 carry alkynyl, amino or phosphino
groups, which should allow an attractive coordination
chemistry. Hence, compounds 8 and 9 were reacted
with a variety of inorganic and organic copper(I) com-
pounds [CuX]n. However, even at −100°C, only off-
white or yellow polymeric products are formed, which
are insoluble in most common organic solvents. IR
spectroscopic studies confirm a p2-coordination of the
alkynyl ligands to the Group 11 metal atom, but the
constitution of the latter complexes could not be as-
signed unequivocally.
115.7(1)
111.4(1)
131.7(2)
102.3(2)
109.8(2)
118.3(2)
107.8(3)
110.2(3)
108.0(3)
115.2(2)
113.6(2)
128.2(3)
110.2(6)
109.1(6)
101.9(5)
106.8(7)
119.0(5)
109.5(5)
125.0(6)
a Estimated S.D. in units of the last significant figure in parentheses.

66
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
Table 3
As typical for hypervalent silicon compounds, com-
pared with tetravalent ones, the 29Si{1H}-NMR reso-
nance signals of compounds 3–11 are shifted upfield
[14]. The presence of two fluoro atoms in compound 6,
as well as two diphenyl–phosphino groups in com-
pound 11 leads to a splitting of the 29Si{1H}-NMR
resonance signals to triplets with 1JSiF=260 Hz and
1JSiP=49.3 Hz, respectively.
In conclusion, the synthesis, reaction behavior, struc-
ture and bonding of highly functionalized hypervalent
silicon compounds was described. For the first time
monodentate bonded alkynyl, amino or phosphino
groups could be introduced in this type of molecules.
Atomic coordinates (×104) and equivalent isotropic thermal parame-
2
3 a
˚
ters for 3c (A ×10 )
Atom
x/a
y/b
z/c
7787(1)
Ueq
Si1
Cl1
Cl2
N1
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
2433(1)
2108(1)
2328(1)
2905(3)
4591(4)
531(4)
2503(1)
688(1)
44(1)
69(1)
70(1)
55(1)
61(1)
61(1)
49(1)
62(1)
68(1)
62(1)
51(1)
40(1)
77(1)
80(1)
8275(1)
6200(1)
7385(2)
7418(3)
7966(3)
8391(3)
8960(3)
9854(3)
10189(3)
9618(3)
8699(2)
8273(4)
6322(3)
2015(1)
4273(2)
4208(3)
2976(3)
3476(3)
3613(3)
2935(4)
2122(3)
1958(3)
2637(3)
5071(3)
4764(4)
5439(4)
7020(4)
7718(4)
6848(4)
5269(4)
4523(3)
2811(5)
1925(5)
3. Experimental section
3.1. General comments
a
Estimated S.D. in units of the last significant figure in parentheses;
Ueq is defined as one-third of the trace of the orthogonalized Uij
tensor.
All reactions were carried out in an atmosphere of
nitrogen, using standard Schlenk techniques. Solvents
were purified by distillation. n-Pentane and
dichloromethane: calcium hydride; diethyl ether and
THF: sodium/benzophenone ketyl; triethylamine and
alcohols: sodium. Water was deoxygenated at 0°C/10−3
mbar and saturated with nitrogen. Chlorosilanes were
distilled from magnesium and stored over magnesium
at 0°C. IR spectra were obtained with a Perkin-Elmer
983G spectrometer as KBr pellets or as film between
NaCl plates. NMR spectra were recorded on a Bruker
AC 200 spectrometer, operating in the Fourier trans-
form mode,1H-NMR spectra were recorded at 200.132
MHz (internal standard relative to CDCl3, l=7.27);
13C{1H}-NMR spectra were recorded at 50.323 MHz
(standard intern, rel. CDCl3, l=77.0); 29Si{1H}-NMR
isomers are formed in which the hydrogen atoms oc-
cupy axial or equatorial positions as well. Due to the
unequal ratio of w(Si–Heq)/w(Si–Hax), whereby the lat-
ter vibration is less intensive for both compounds, one
can conclude that the equatorial positions in the trigo-
nal bipyramid are preferentially occupied. Similar re-
sults were concluded by Corriu et al. on
dihydridosilanes of type [C6H4CH2N(CH3)2-2](R)SiH2
and [C10H6CH2N(CH3)2-8](R)SiH2 (R=C6H5, h-
C10H7) by dynamic NMR studies [9]. Compared with
tetravalent silanes [13], the Si–H frequencies in the
penta-coordinated silicon compounds 7a and 7b are
shifted to lower wavenumbers.
However, for compound 7a the formation of differ-
ent isomers as revealed by IR spectroscopic studies is
Table 4
Atomic coordinates (×104) and equivalent isotropic thermal parame-
1
not observed by H-NMR studies down to −100°C.
2
3 a
˚
ters for 3d (A ×10 )
Similar observations were made for all synthesized
compounds with exception of compounds 3 and 6. This
phenomenon can be explained by the increased ten-
dency of the halide substituents in accepting electron
density as compared to alkyl, alkenyl, alkynyl and
alkoxy groupings as well as H atoms.
Atom
x/a
y/b
8072(2)
5831(2)
7086(2)
10336(8)
8411(9)
7764(10)
8120(11)
9079(10)
9724(9)
z/c
Ueq
Si1
Cl1
Cl2
N1
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
1043(3)
2560(3)
7995(2)
8266(2)
8091(2)
7546(5)
6452(6)
5980(6)
4832(6)
4134(6)
4564(7)
5738(6)
6282(7)
8189(8)
7711(7)
9390(6)
9892(7)
29(1)
39(1)
37(1)
37(2)
32(2)
36(2)
41(2)
43(2)
38(2)
33(2)
40(2)
48(2)
44(2)
35(2)
43(2)
−1826(2)
−495(9)
2107(10)
3901(10)
4566(10)
3445(13)
1657(12)
1035(11)
−838(11)
−2418(12)
937(13)
Moreover, the silicon atom in compound 7b is sur-
rounded by a benzyl, vinyl and methyl unit as well as
by a H atom and is thus chiral. The chirality is directly
reflected in diastereotopic methylene protons of the
CH2N(CH3)2 entity, which is observed by the existence
of two resonance signals at 3.59 and 3.61 ppm, respec-
tively. However, of the insignificantly magnetic differ-
ence of the two protons, a splitting into doublets, which
9420(9)
10142(10)
10759(12)
11664(9)
9020(9)
2
1782(11)
3s42(12)
should be caused by a JHH coupling, is not observed.
8841(11)
In contrast, the chirality of 3e causes the magnetically
inequivalent methylene protons of the CH2N(CH3)2
unit, which leads to a separation of two doublets
(2JHH=3.3 Hz), already at 25°C.
a
Estimated S.D. in units of the last significant figure in parentheses;
Ueq is defined as one-third of the trace of the orthogonalized Uij
tensor.

M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
67
spectra at 39.763 MHz (standard extern, rel. Si(CH3)4,
l=0) and 31P{1H}-NMR spectra at 81.015 MHz (stan-
dard extern, rel. 85% H3PO4, with P(OMe)3 l=139
ppm). Chemical shifts are reported in l units (ppm)
downfield from TMS with the solvent as reference
signal. FD and EI mass spectra were recorded on a
Finnigan 8400 mass spectrometer, operating in the pos-
itive-ion mode. Melting points were determined using
analytically pure samples, sealed off in nitrogen purged
capillaries on a Gallenkamp MFB 595 010 M melting
point apparatus. Microanalyses were performed by the
143.0 (C6H4). EI MS m/e (rel. int.): M+, 227 (26);
M
+ −CH3,
212
(86);
M
+ −Cl,
192
(12);
CH2N(CH3)2+, 58 (100). Anal. Calc. for C11H18NClSi
(227.79): C, 58.00; H, 7.96. Found: C, 57.87; H, 7.70%.
3.2.3. Data for [C6H4CH2N(CH3)2-2](CH3)SiCl2 (3c)
Yield: 24.0 g (96.7 mmol, 97%, rel. (CH3)SiCl3). M.p.
1
94°C. H-NMR (CDCl3): l 1.03 (s, 3 H, SiCH3), 2.28
(s, 6 H, NCH3), 3.70 (s, 2 H, CH2), 7.1–7.2 (m, 1 H,
C6H4), 7.3–7.4 (m, 2 H, C6H4), 8.2–8.3 (m, 1 H, C6H4).
13C{1H}-NMR (CDCl3): l 9.3 (SiCH3), 44.9 (NCH3),
62.7 (CH2), 126.1, 127.2, 131.1, 132.9, 138.6, 144.0
(C6H4) 29Si{1H}-NMR (CDCl3): l −24.1. EI MS m/e
(rel. int.): M+, 248 (66); M+ −CH3, 233 (6); M+ −Cl,
213 (44); M+ −2Cl, 178 (100); C6H5Si+, 105 (45).
Anal. Calc. for C10H15NCl2Si (248.21): C, 48.39; H,
6.09; N, 5.64. Found: C, 48.84; H, 6.58; N, 5.52%.
Organisch-Chemisches
Heidelberg.
Institut
der
Universita¨t
3.2. General procedure for the synthesis of compounds
3a–e
According to the procedure described by van Koten
n
and coworkers [7], 100 mmol of BuLi (40 ml 2.5 M
3.2.4. Data for [C6H4CH2N(CH3)2-2](H2CꢀCH)SiCl2
(3d)
solution in n-hexane) are added dropwise to 100 mmol
C6H5CH2N(CH3)2-2 (13.5 g) in 300 ml of diethyl ether
at −30°C. The reaction mixture is allowed to warm to
25°C and stirred at this temperature for 7 days. The
formed colorless suspension of LiC6H4CH2N(CH3)2-2 is
added at −30°C, via a teflon cannula, to 100 mmol of
the appropriate chlorosilane (3a: 17.0 g SiCl4; 3b: 12.9 g
Yield: 21.5 g (83.0 mmol, 83%, rel. (H2CꢀCH)SiCl3) .
1
M.p. 104°C. IR (NaCl, cm−1): wCꢀC=1589 (m). H-
NMR (CDCl3): l 2.26 (s, 6 H, NCH3), 3.70 (s, 2 H,
CH2), 5.9–6.1 (m, 2 H, C2H3), 6.3–6.5 (m, 1 H, C2H3),
7.1–7.2 (m, 1 H, C6H4), 7.3–7.4 (m, 2 H, C6H4),
8.3–8.4 (m, 1 H, C6H4). 13C{1H}-NMR (CDCl3): l 45.2
(NCH3), 62.5 (CH2), 125.9 (C6H4), 127.4 (C6H4), 130.4
(C2H3), 131.4 (C6H4), 131.9 (C6H4), 136.1 (C2H3), 139.2
(C6H4), 144.0 (C6H4). 29Si{1H}-NMR (CDCl3): l −
41.0. EI MS m/e (rel. int.): M+, 259 (10); M+ −CH3,
255 (8); M+ −Cl, 225 (44); M+ −N(CH3)2, 216 (65);
N(CH3)3+, 59 (100). Anal. Calc. for C11H15NCl2Si
(260.23): C, 50.77; H, 5.81; N, 5.38. Found: C, 50.92;
H, 6.05; N, 5.17%.
(CH3)2SiCl2; 3c: 15.0
g (CH3)SiCl3; 3d: 16.2 g
(H2CꢀCH)SiCl3; 3e: 14.1 g (CH3)(H2CꢀCH)SiCl2) dis-
solved in 200 ml of diethyl ether. The reaction mixture
is allowed to warm to 25°C overnight. After filtration
through a pad of Celite, all volatile materials are re-
moved in vacuum and the obtained residues are crystal-
lized from concentrated dichloromethane/n-pentane
(3a–c; ratio 5:1) or diethyl ether/n-pentane (3d; ratio
1:1) solutions at −30°C. Compound 3e is purified by
vacuum distillation.
3.2.5. Data for [C6H4CH2N(CH3)2-2](CH3)
(H2CꢀCH)SiCl (3e)
3.2.1. Data for [C6H4CH2N(CH3)2-2/SiCl3 (3a)
Yield:
17.6
g
(73.6
mmol,
74%,
rel.
Yield: 25.0 g (93.1 mmol, 93%, rel. SiCl4). M.p.
1
(CH3)(H2CꢀCH)SiCl2). B.p. 115–118°C/10−2 mbar. IR
(NaCl, cm−1): wCꢀC=1588 (s). 1H-NMR (CDCl3): l
0.79 (s, 3 H, SiCH3), 2.15 (s, 6 H, NCH3), 3.51 (br s, 1
H, CH2), 3.60 (br s, 1 H, CH2), 5.84 (dd, 2JHH=3.3 Hz,
112°C. H-NMR (CDCl3): l 2.46 (s, 6 H, NCH3), 3.83
(s, 2 H, CH2), 7.1–7.2 (m, 1 H, C6H4), 7.4–7.5 (m, 2 H,
C6H4), 8.2–8.3 (m,
1
H, C6H4). 13C{1H}-NMR
(CDCl3): l 46.1 (NCH3), 61.9 (CH2), 125.5, 128.0,
132.2, 132.9, 139.3, 142.1 (C6H4). 29Si{1H}-NMR
(CDCl3): l −62.6. EI MS m/e (rel. int.): M+, 267 (13);
2
3JHH=19.9 Hz, 1 H, C2H3), 6.02 (dd, JHH=3.3 Hz,
3
3JHH=14.5 Hz, 1 H, C2H3), 6.41 (dd, JHH=14.5 Hz,
3JHH=19.9 Hz, 1 H, C2H3), 7.1–7.2 (m, 1 H, C6H4),
7.3–7.4 (m, 2 H, C6H4), 8.2–8.4 (m, 1 H, C6H4).
13C{1H}-NMR (CDCl3): l 2.5 (SiCH3), 44.9 (NCH3),
63.7 (CH2), 126.5 (C6H4), 126.9 (C6H4), 129.9 (C2H3),
130.3 (C6H4), 133.5 (C6H4), 137.1 (C2H3), 138.3 (C6H4),
144.6 (C6H4). 29Si{1H}-NMR (CDCl3): l −21.0. EI
MS m/e (rel. int.): M+, 239 (12); M+ −CH3, 224 (13);
M
+ −Cl, 232 (62); M+ −2Cl, 197 (12); CH2N(CH3)2+
, 58 (100). Anal. Calc. for C9H12NCl3Si (268.63): C,
40.24; H, 4.50. Found: C, 40.01; H, 3.99%.
3.2.2. Data for [C6H4CH2N(CH3)2-2](CH3)2SiCl (3b)
Yield: 23.0 g [100.0 mmol, 100%, rel. (CH3)2SiCl2].
1
M.p. 98°C. H-NMR (CDCl3): l 0.83 (s, 6 H, SiCH3),
M
+ −Cl, 204 (39); M+ −C2H3–CH3, 196 (100); M+
2.16 (s, 6 H, NCH3), 3.64 (s, 2 H, CH2), 7.1–7.2 (m, 1
H, C6H4), 7.4–7.5 (m, 2 H, C6H4), 8.2–8.3 (m, 1 H,
C6H4). 13C{1H}-NMR (CDCl3): l 3.5 (SiCH3), 46.5
(NCH3), 60.0 (CH2), 125.7, 127.9, 132.6, 132.9, 139.4,
−Cl–C2H3, 178 (60); (C6H5)(C2H3)Si+, 132 (22);
(C6H5)Si+, 105 (15). Anal. Calc. for C12H18NClSi
(239.81): C, 60.10; H, 7.56. Found: C, 59.25; H, 8.02%.

68
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
3.3. X-ray structure determinations of compounds 3c and
3d [16]
3.5. General procedure for the synthesis of compounds
5a–d
The structures of compounds 3c and 3d were deter-
mined from single crystal X-ray diffraction data, which
were collected using a Siemens R3 m/V (Nicolet Syntex)
diffractometer. Crystallographic data for 3c and 3d are
given in Table 1. All structures were solved by direct
methods (SHELX-97) [17]. An initial empirical absorp-
tion correction was applied. The structures of com-
pounds 3c and 3d were refined by the least-squares
method based on F2 with all reflections (SHELX-97). All
non-H atoms were refined anisotropically; the H atons
were placed in calculated positions. The structure plots
have been made using ZORTEP [18].
A total of 50.0 ml of methanol (39.5 g, 1.23 mol),
ethanol (39.5 g, 0.86 mol) or i-propanol (39.0 g, 0.65 mol)
and 40 ml of triethylamine (29.2 g, 0.29 mol) are mixed
and cooled to 0°C. To this mixture, 15.0 mmol
[C6H4CH2N(CH3)2-2](C2H3)(R)SiCl (3d: R=Cl, 3.9 g;
3e: R=CH3, 3.6 g) are added slowly in four steps. An
exothermic reaction is observed each time. To complete
the reaction, the mixture is refluxed for 30 min and then
filtered through a pad of Celite. After removal of all
volatile materials under vacuum, the colorless oils ob-
tained are purified by vacuum distillation.
3.5.1. Data
3.4. General procedure for the synthesis of compounds 4a
and 4b
for[C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)Si(OCH3) (5a)
Yield: 2.3 g (9.8 mmol, 65%, rel. 3e). B.p. 130°C/10−1
mbar (ball tube distillation). IR (NaCl, cm−1): wCH
=
10.0 mmol of [C6H4CH2N(CH3)2-2](H2CꢀCH)(R)
SiCl (3d: R=Cl, 2.6 g; 3e: R=CH3, 2.4 g) are dissolved
in 50 ml of THF and 2 ml of water are added in one
portion at 25°C. The reaction mixture is refluxed for 30
min and then all volatile materials are removed under
vacuum at 25°C. The residue obtained is dissolved in 50
ml of dichloromethane and dried over MgSO4. After
removing the solvent under vacuum, compounds 4a and
4b are obtained as a colorless oil and powder, respec-
tively.
3044 (s), 2965 (vs), 2938 (vs), 2897 (s), 2851 (vs), 2811 (vs);
wCꢀC=1587 (m); wSiO=1076 (vs). H-NMR (CDCl3): l
1
0.59 (s, 3 H, SiCH3), 2.10 (s, 6 H, NCH3), 3.36 (d,
2JHH=13.1 Hz, 1 H, CH2), 3.46 (s, 3 H, OCH3), 3.53 (d,
2
2JHH=13.1 Hz, 1 H, CH2), 5.79 (dd, JHH=4.3 Hz,
2
3JHH=19.7 Hz, 1 H, C2H3), 5.98 (dd, JHH=4.3 Hz,
3
3JHH=15.4 Hz, 1 H, C2H3), 6.27 (dd, JHH=15.4 Hz,
3JHH=19.7 Hz, 1 H, C2H3), 7.2–7.3 (m, 3 H, C6H4),
7.7–7.8 (m, 1 H, C6H4). 13C{1H}-NMR (CDCl3): l −0.8
(SiCH3), 44.8 (NCH3), 50.4 (OCH3), 64.1 (CH2), 126.3,
128.2, 129.3, 139.4, 132.5, 135.7, 136.3, 145.7 (C2H3 and
C6H4). 29Si{1H}-NMR (CDCl3): l −12.4. EI MS m/e
3.4.1. Data for {[C6H4CH2N(CH3)2-2](H2CꢀCH)SiO}n
(4a)
(rel. int.): M+, 235 (6); M+ −CH3, 220 (17); M+
−
Yield: 1.71 g (8.3 mmol, 83%, rel. 3b). Mol. wt.: 600 g
mol−1 (cryoscopic measurement in benzene [15]); n˜ =
2.9. IR (NaCl, cm−1): wOH=3381 (vs), wCꢀC=1594 (w),
CH3–C2H4, 192 (43); M+ −2CH3–C2H3, 178 (100).
Anal. Calc. for C13H21NOSi (235.40): C, 66.33; H, 8.99.
Found: C, 66.13; H, 8.78%.
1
wSiO=1080 (vs). H-NMR (CDCl3): l 2.0–2.3 (m, 6 H,
NCH3), 3.4–3.7 (m, 2 H, NCH2), 5.6–6.4 (m, 3 H, C2H3),
7.0–8.0 (m, 4 H, C6H4). Anal. Calc. for [C11H15ONSi]n
(205.32)n: C, 64.35; H 7.36. Found: C, 63.85; H, 6.98%.
3.5.2. Data for
[C6H4CH2N(CH3)2-2](H2CꢀCH)Si(OCH3)2 (5b)
Yield: 1.8 g (7.2 mmol, 48%, rel. 3d). B.p. 118°C/10−1
mbar. IR (NaCl, cm−1): wCH=3047 (s), 2967 (s) 2933
(vs), 2948 (m), 2827 (s), 2811 (s), 2771 (s); wCꢀC=1588
3.4.2. Data for
1
{[C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)Si }2O (4b)
Yield: 1.70 g (4.0 mmol, 80%, rel. 3e). IR (KBr, cm−1):
wCH=2944 (vs), 2817 (vs), 2777 (vs); wCꢀC=1588 (w);
wSiO=1044 (vs). 1H-NMR (CDCl3): l 0.53 (s, 6 H,
SiCH3), 2.26 (s, 12 H, NCH3), 3.33 (d, 2JHH=12.2 Hz, 2
H, NCH2), 3.83 (d, 2JHH=12.2 Hz, 2 H, NCH2), 5.8–6.5
(m, 6 H, C2H3), 7.2–7.6 (m, 6 H, C6H4), 7.8–7.9 (m, 2 H,
C6H4). 13C{1H}-NMR (CDCl3): l −1.5 (SiCH3), 45.0
(NCH3), 64.2 (NCH2), 126.0–145.0 (C2H3 and C6H5).
29Si{1H}-NMR (CDCl3): l −20.3. FAB MS m/e (rel.
int.): M+, 425 (9); M+ −CH3, 410 (19); M+ −C2H3,
(m); wSiO 1084 (vs). H-NMR (CDCl3): l 2.16 (s, 6 H,
NCH3), 3.51 (s, 2 H, CH2), 3.59 (s, 6 H, OCH3), 5.8–5.9
(m, 1 H, C2H3), 6.0–6.2 (m, 2 H, C2H3), 7.3–7.4 (m, 3 H,
C6H4), 7.8–7.9 (m, 1 H, C6H4). 13C{1H}-NMR (CDCl3):
l 44.7 (NCH3), 50.1 (OCH3), 63.8 (CH2), 126.1, 128.0,
129.9, 131.7, 133.4, 133.7, 136.5, 146.5 (C2H3 and C6H4).
29Si{1H}-NMR (CDCl3): l −32.67. EI MS m/e (rel.
int.): M+, 251 (24); M+ −CH3, 236 (50); M+ −C2H3–
CH4, 208 (100). Anal. Calc. for C13H21NO2Si (251.40): C,
62.11; H, 8.42. Found: C, 62.48; H, 8.89%.
398 (10);
M
+ −N(CH3)2–C2H3–CH3, 338 (79);
3.5.3. Data for [C6H4CH2N(CH3)2-2](H2Cꢀ
CH)Si(OC2H5)2 (5c)
[C6H4CH2N(CH3)2](C2H3)(CH3)Si+, 204 (60). Anal.
Calc. for C24H36N2OSi2 (424.73): C, 65.11; H, 8.65
Found: C, 65.65; H, 7.99%.
Yield: 2.3 g (8.3 mmol, 55%, rel. 3d). B.p. 110°C/10−
2 mbar. IR (NaCl, cm−1): wCH=3048 (s), 2966 (s),

M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
69
2937 (vs), 2873 (m), 2810 (s), 2768 (s); wCꢀC=1588 (m);
22.0 Hz), 131.3, 134.2, 137.5, 145.2 (C2H3 and C6H4).
1
3
1
29Si{1H}-NMR (CDCl3): l −62.6 (t, JSiF=258.8 Hz).
wSiO=1079 (vs). H-NMR (CDCl3): l 1.20 (t, JHH
=
EI MS m/e (rel. int.): M+, 227 (39); M+ −CH3, 212
(41); M+ −C2H3, 200 (22); M+ −C2H3–CH4, 184
(57); M+ −C2H3–CH3−2F, 132 (23); CH2N(CH3)2+,
58 (100). Anal. Calc. for C11H15NF2Si (227.33): C,
58.12; H, 6.65. Found: C, 57.73; H, 7.03%.
7.0 Hz, 6 H, OCH2CH3), 2.16 (s, 6 H, NCH3), 3.48 (s,
2 H, NCH2), 3.77 (q, JHH=7.0 Hz, 4 H, OCH2CH3),
3
5.7–5.9 (m, 1 H, C2H3), 6.0–6.1 (m, 2 H, C2H3),
7.1–7.2 (m, 1 H, C6H4), 7.3–7.4 (m, 2 H, C6H4),
7.7–7.8 (m, 1 H, C6H4). 13C{1H}-NMR (CDCl3): l 18.2
(OCH2CH3), 45.0 (NCH3), 58.0 (OCH2CH3), 63.8
(NCH2), 126.0, 128.2, 129.9, 132.6, 133.9, 134.2, 136.4,
146.4 (C2H3 and C6H4). 29Si{1H}-NMR (CDCl3): l
3.7. Synthesis of [C6H4CH2N(CH3)2-2](H2CꢀCH)SiH2
(7a) from 5b
−40.0. EI MS m/e (rel. int.): M+, 279 (20); M+
CH3, 264 (52); M+ −CH3–C2H4, 236 (100); M+
−
−
At 0°C 31.0 g (124.0 mmol) of [C6H4CH2N(CH3)2-
2](H2CꢀCH)Si(OCH3)2 (5b) are dissolved in 300 ml of
diethyl ether and added slowly to a suspension of 2.6 g
(68.4 mmol) LiAlH4 in 500 ml of diethyl ether. The
gray slurry is slowly warmed to 25°C and the solvent is
distilled off. To the residue obtained 400 ml of n-pen-
tane are added and filtered through a pad of Celite.
After removal of the solvent the colorless oil is further
purified by vacuum distillation (64–68°C/10−1 mbar)
to yield 14.8 g (63%, 77.0 mmol, rel. 5b) of 7a.
OCH2CH3, 234 (37). Anal. Calc. for C15H25NO2Si
(279.46): C, 64.47; H, 9.02. Found: C, 63.99; H, 9.60%.
3.5.4. Data for [C6H4CH2N(CH3)2-2](H2Cꢀ
CH)Si(OiC3H7)2 (5d)
Yield: 2.5 g (8.1 mmol, 54%, rel. 3d). IR (NaCl,
cm−1): wCH=3049 (m), 2965 (vs), 2936 (vs), 2882 (m),
2810 (s), 2767 (s); wCꢀC=1588 (m); wSiO=1029 (vs).
1H-NMR (CDCl3): l 1.3 [m1, 12 H, OCH(CH3)2], 2.25
(s, 6 H, NCH3), 3.66 (s, 2 H, NCH2), 4.28 [m, 2 H,
OCH(CH3)2], 6.0–6.2 (m, 3 H, C2H3), 7.3–7.6 (m, 3 H,
IR (NaCl, cm−1): wCH=3045 (s), 2969 (s), 2937 (s),
2852 (s), 2817 (s), 2781 (s); wSiH=2135 (vs), 2081 (m);
wCꢀC=1586 (s). 1H-NMR (CDCl3): l 2.35 (s, 6 H,
C6H4), 7.8–7.9 (m,
1
H, C6H4). 13C{1H}-NMR
(CDCl3): l 25.02 [OCH(CH3)2], 25.62 [OCH(CH3)2],
45.2 (NCH3), 63.5 (NCH2), 65.2 [OCH(CH3)2], 125.8,
128.1, 129.9, 133.2, 134.5, 134.9, 136.2, 146.0 (C2H3 and
C6H4). 29Si{1H}-NMR (CDCl3): l −42.3. EI MS m/e
3
NCH3), 4.73 (d, JHH=3.2 Hz, 2 H, SiH), 3.67 (s, 2 H,
2
3
CH2), 6.13 (dd, JHH=4.4 Hz, JHH=19.5 Hz, 1 H,
2
3
C2H3), 6.28 (dd, JHH=4.4 Hz, JHH=14.1 Hz, 1 H,
C2H3), 6.4–6.6 (m, 1 H, C2H3), 7.2–7.3 (m, 1 H, C6H4),
7.4–7.5 (m, 2 H, C6H4), 7.8–7.9 (m, 1 H, C6H4).
13C{1H}-NMR (CDCl3): l 46.3 (NCH3), 61.9 (CH2),
126.6, 126.9, 129.4, 133.2, 133.5, 136.9, 139.5, 145.7
(C2H3 and C6H4). 29Si{1H}-NMR (CDCl3): l −46.2.
EI MS m/e (rel. int.): M+, 191 (36); M+ −CH3, 176
(57); M+ −C2H3, 164 (64); M−CH3–C2H4, 148 (98);
(C6H4CH2)Si(C2H3)+, 145 (100). Anal. Calc. for
C11H17NSi (191.34): C, 69.05; H, 8.95. Found: C, 68.98;
H, 9.04%.
(rel. int.): M+, 307 (33); M+ −CH3, 292 (64); M+
−
CH(CH3)2, 264 (100); M+ −OCH(CH3)2, 248 (58).
Anal. Calc. for C17H29NO2Si (307.51): C, 66.40; H,
9.50. Found: C, 66.61; H, 9.16%.
3.6. Synthesis of [C6H4CH2N(CH3)2-2](H2CꢀCH)SiF2
(6)
Freshly distilled BF3 ·O(C2H5)2 [870 mg (6.1 mmol)]
are added dropwise to a solution of 1.53 g (6.1 mmol)
[C6H4CH2N(CH3)2-2](H2CꢀCH)Si(OCH3)2 (5b) in 30
ml of n-pentane at 25°C. The reaction mixture is stirred
for 30 min and then all volatile materials are removed
under vacuum. The yellow oil obtained is purified by
ball tube distillation (temperature of the air bath
170°C/10−1 mbar). 1.1 g (4.84 mmol, 79%, rel. com-
pound 5b) of 6 are obtained as a colorless oil.
3.8. Synthesis of
[C6H4CH2N(CH3)2-2](H2CꢀCH)(R)SiH (7) from 3
A solution of 16.0 g (62 mmol) [C6H4CH2N(CH3)2-
2](H2CꢀCH)SiCl2 (3d) in 300 ml of diethyl ether or 30.0
g (124 mmol) [C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)-
SiCl (3e) in 500 ml of diethyl ether is added dropwise to
a suspension of 2.6 g (68.4 mmol) LiAlH4 in 500 ml of
diethyl ether at 0°C. The reaction mixture is slowly
warmed to 25°C and then refluxed for 1 h. All volatile
materials are removed at 0°C and the residue obtained
extracted with a total of 500 ml of n-pentane. Filtration
through a pad of Celite and following distillation under
vacuum produced the compounds [C6H4CH2N(CH3)2-
2](H2CꢀCH)(R)SiH (7a: R=H; 7b: R=CH3) as color-
less oils.
IR (NaCl, cm−1): wCH=3053 (s), 2998 (s), 2946 (s),
2868 (s), 2835 (s), 2789 (m); wCꢀC=1591 (s); wSiF=853
1
(vs). H-NMR (CDCl3): l 2.30 (s, 6 H, NCH3), 3.62 (s,
2 H, NCH2), 6.0–6.1 (m, 3 H, C2H3), 7.1–7.2 (m, 1 H,
C6H4), 7.3–7.4 (m, 2 H, C6H4), 7.9–8.0 (m, 1 H, C6H4).
13C{1H}-NMR (CDCl3): l 45.2 (NCH3), 62.9 (NCH2),
3
3
125.5, 127.2, 131.1 (t, JCF=23.0 Hz), 132.8 (t, JCF
=
i
1 Hindered rotation of the C3H7 units at 25°C.
2 Due to the hindered rotation of the iC3H7 units at 25°C two
resonance signals for the methyl carbon atoms are observed.

70
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
3.8.1. Data for [C6H4CH2N(CH3)2-2](H2CꢀCH)SiH2
(7a)
Yield: 6.7 g (35.3 mmol, 57%, rel. 3d). For spectro-
scopic and analytical data see Section 3.7.
(SiCꢁC), 123.0, 127.9, 128.5, 128.8, 129.0, 129.7, 132.0,
136.6, 137.5, 146.0 (C6H4, C6H5). 29Si{1H}-NMR
(CDCl3): l −24.2. EI MS m/e (rel. int.): M+, 293 (34);
M
+ −CH3, 278 (32); M+ −N(CH3)2, 250 (100); M+
−N(CH3)2–CH3, 235 (23); M+ −C2C6H5, 191 (6);
M
+ −C2C6H5–CH3, 176 (68); HC2C6H5+, 102 (12).
3.8.2. Data for [C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)
SiH (7b)
Anal. Calc. for C19H23NSi (293.48): C, 77.76; H, 7.90.
Found: C, 77.94; H, 8.13%.
Yield: 14.3 g (70.0 mmol, 54%, rel. 3d). B.p. 63°C/
10−1 mbar. IR (NaCl, cm−1): wCH=3043(s), 2997 (s),
3.9.2. Data for [C6H4CH2N(CH3)2-2](CH3)2Si[Cꢁ
CSi(CH3)3] (8b)
2965 (s), 2937 (s), 2851 (s), 2817 (vs), 2773 (vs); wSiH
=
2133 (vs), 2094 (m); wCꢀC=1586 (m). 1H-NMR
3
Yield: 3.90 g (13.5 mmol, 67%, rel. 3b). B.p. 98°C/
(CDCl3): l 0.55 (d, JHH=3.6 Hz, 3 H, SiCH3), 2.29 (s,
1
10−1 mbar. IR (NaCl, cm−1): wCꢁC=2102 (vw). H-
6 H, NCH3), 3.59 (s, 1 H, CH2), 3.61 (s, 1 H, CH2),
3
3
NMR (CDCl3): l 0.26 (s, 9 H, SiCH3), 0.51 (s, 6 H,
SiCH3), 2.24 (s, 6 H, NCH3), 3.66 (s, 2 H, CH2), 7.3–7.5
(m, 3 H, C6H4), 7.8–7.9 (m, 1 H, C6H4). 13C{1H}-NMR
(CDCl3): l −0.1 (SiCH3), 0.5 (SiCH3), 44.9 (NCH3),
64.5 (CH2), 114.5 (CꢁC), 114.8 (CꢁC), 126.4, 128.6,
129.4, 135.3, 135.9, 145.8 (C6H4). 29Si{1H}-NMR
(CDCl3): l −24.4 [Si(CH3)3], −30.6 [Si(CH3)2]. EI
MS m/e (rel. int.): M+, 289 (1); M+ −CH3, 274 (17);
M−N(CH3)2, 246 (57); M+ −Si(CH3)3, 216 (11); M+
−Si(CH3)3–CH3, 201 (9); M+ −C2Si(CH3)3–CH3, 176
(100). Anal. Calc. for C16H27NSi2 (289.57): C, 66.37; H,
9.40. Found: C, 66.16; H, 9.43%.
4.75 (dq, JHH=2.6 Hz, JHH=3.6 Hz, 1 H, SiH), 5.96
2
3
(dd, JHH=4.2 Hz, JHH=19.9 Hz, 1 H, C2H3), 6.19
(dd, JHH=4.2 Hz, JHH=14.4 Hz, 1 H, C2H3), 6.49
2
3
3
3
3
(ddd, JHHSi=2.6 Hz, JHH=14.4 Hz, JHH=19.9 Hz,
1 H, C2H3), 7.3–7.4 (m, 3 H, C6H4), 7.7–7.8 (m, 1 H,
C6H4). 13C{1H}-NMR (CDCl3): l −4.4 (SiCH3), 44.5
(NCH3), 64.6 (CH2), 126.5 (C6H4), 128.3 (C6H4), 129.1
(C6H4), 132.4 (C6H4), 136.0 (C6H4), 136.2 (C2H3), 137.8
(C6H4), 145.8 (C2H3). 29Si{1H}-NMR (CDCl3): l −
31.9. EI MS m/e (rel. int.): M+, 205 (13); M+ −CH3,
190 (53); M+ −C2H3, 178 (14); M+ −CH3–C2H4, 162
(100); M+ −3CH3, 160 (61); (C6H4CH2)Si(C2H3)+,
145 (77). Anal. Calc. for C12H19NSi (205.37): C, 70.16;
H, 9.32. Found: C, 69.83; H, 9.24%.
3.9.3. Data for [C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)
Si(CꢁCC6H5) (8c)
Yield: 4.90 g (16.1 mmol, 80%, rel. 3e). B.p. 210°C/
3.9. General procedure for the synthesis of compounds
8a–d and 9a–c
10−1 mbar (ball tube distillation). IR (NaCl, cm−1):
1
wCꢀC=2155 (vs); wCꢀC=1587 (s). H-NMR (CDCl3): l
0.80 (s, 3 H, SiCH3), 2.32 (s, 6 H, NCH3), 3.75 (s, 2 H,
CH2), 6.2–6.3 (m, 2 H, C2H3), 6.4–6.6 (m, 1 H, C2H3),
7.4–7.5 (m, 6 H, C6H4, C6H5), 7.6–7.7 (m, 2 H, C6H4,
C6H5), 8.1–8.2 (m, 1 H, C6H4) 13C{1H}-NMR (CDCl3):
l −1.2 (SiCH3), 44.9 (NCH3), 64.5 (CH2), 93.2
(SiCꢁC), 106.3 (SiCꢁC), 123.4, 126.5, 128.1, 128.3,
128.5, 129.5, 131.8, 132.9, 134.1, 135.5, 136.7, 145.9
(C2H3, C6H4, C6H5). 29Si{1H}-NMR (CDCl3): l −36.5.
EI MS m/e (rel. int.): M+, 305 (12); M+ −CH3, 290
(33); M+ −N(CH3)2, 262 (100); M+ −N(CH3)2–C2H3,
234 (31); M+ −C2C6H5–CH3, 188 (87). Anal. Calc. for
C20H23NSi (305.49): C, 78.63; H, 7.59. Found: C, 77.41;
H, 7.68%.
20.0 mmol HCꢁCR (R=C6H5: 2.04 g; R=Si(CH3)3:
1.96 g) in 50 ml of diethyl ether are lithiated using
n
equimolar amounts of a 2.5 M BuLi solution in n-hex-
ane at 0°C. The obtained LiCꢁCR reagents are warmed
to 25°C and then slowly added to 20.0 mmol of
[C6H4CH2N(CH3)2-2](CH3)(R)SiCl (3b: R=CH3, 4.56
g; 3e: R=H2CꢀCH, 4.79 g; synthesis of compounds
8a–d) or 10.0 mmol of [C6H4CH2N(CH3)2-2](R)SiCl2
(3c: R=CH3, 2.48 g; 3d: R=H2CꢀCH, 2.60 g; synthe-
sis of compounds 9a–c) at −30°C. The reaction mix-
ture is allowed to warm to 25°C. After addition of 200
ml of n-pentane the suspension is filtered through a pad
of Celite. While compounds 8a and 9a can further be
purified by crystallization from concentrated diethyl
ether/n-pentane (1:1) solution at −30°C, compounds
8b–d, 9b and 9c are best purified by vacuum distillation.
3.9.4. Data for [C6H4CH2N(CH3)2-2](H2CꢀCH)(CH3)
Si[CꢁCSi(CH3)3] (8d)
Yield: 4.20 g (13.9 mmol, 70%, rel. 3e). B.p. 102°C/
5×10−2 mbar. IR (NaCl, cm−1): wCꢁC=2102 (vw);
wCꢀC=1587 (s). 1H-NMR (CDCl3): l 0.36 (s, 9 H,
SiCH3), 0.66 (s, 3 H, SiCH3), 2.28 (s, 6 H, NCH3), 3.69
3.9.1. Data for [C6H4CH2N(CH3)2-2](CH3)2Si(Cꢁ
CC6H5) (8a)
Yield: 5.0 g (17 mmol, 85%, rel. 3b). IR (KBr, cm−1):
wCꢁC=2160 (vs). 1H-NMR (CDCl3): l 0.61 (s, 6 H,
SiCH3), 2.25 (s, 6 H, NCH3), 3.70 (s, 2 H, CH2), 7.3–7.4
(m, 6 H, C6H4, C6H5), 7.5–7.6 (m, 2 H, C6H4, C6H5),
7.8–7.9 (m, 1 H, C6H4). 13C{1H}-NMR (CDCl3): l 0.5
(SiCH3), 44.8 (NCH3), 64.5 (CH2), 94.2 (SiCꢁC), 105.6
2
3
(s, 2 H, CH2), 6.10 (dd, JHH=4.3 Hz, JHH=19.6 Hz,
2
3
1 H, C2H3), 6.21 (dd, JHH=4.3 Hz, JHH=14.6 Hz, 1
3
3
H, C2H3), 6.48 (dd, JHH=14.6 Hz, JHH=19.6 Hz, 1
H, C2H3), 7.3–7.4 (m, 3 H, C6H4), 7.9–8.0 (m, 1 H,
C6H4). 13C{1H}-NMR (CDCl3): l −1.3 (SiCH3), −0.1
(SiCH3), 44.8 (NCH3), 64.4 (CH2), 112.5 (CꢁC),

M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
71
114.9 (CꢁC), 126.4, 128.4, 129.5, 132.9, 133.9, 136.6,
136.8, 145.9 (C2H3, C6H4) 29Si{1H}-NMR (CDCl3): l
−24.3 [Si(CH3)3], −37.8 (SiCH3). EI MS m/e (rel.
(CDCl3): l 0.27 (s, 18 H, SiCH3), 2.20 (s, 6 H, NCH3),
3.67 (s, 2 H, CH2), 6.1–6.2 (m, 3 H, C2H3), 7.2–7.3 (m,
1 H, C6H4), 7.3–7.4 (m, 2 H, C6H4), 8.1–8.2 (m, 1 H,
C6H4). 13C{1H}-NMR (CDCl3): l −0.2 (SiCH3), 44.4
(NCH3), 63.6 (CH2), 110.1 (CꢁC), 114.3 (CꢁC), 126.6,
127.5, 129.9, 133.9, 135.1, 136.8, 137.8, 146.3 (C2H3,
C6H4). 29Si{1H}-NMR (CDCl3): l −18.7 (SiCH3), −
62.3 [Si(C2H3)]. EI MS m/e (rel. int.): M+, 384 (18);
int.): M+, 301 (10); M+ −CH3, 286 (28); M+
−
N(CH3)2, 258 (100); M+ −N(CH3)2–C2H3, 230 (12);
M
+ −C2Si(CH3)3–CH3, 188 (95). Anal. Calc. for
C17H27NSi2 (301.58): C, 67.71; H, 9.02. Found: C,
67.86; H, 8.73%.
M
+ −CH3, 369 (23); M+ −CH3–C2H3, 342 (32); M+
3.9.5. Data for [C6H4CH2N(CH3)2-2](CH3)
Si(CꢁCC6H5)2 (9a)
−Si(CH3)3, 311 (25); M+ −C2Si(CH3)3, 287 (31); M+
−HC2Si(CH3)3–CH3, 270 (100); M+ −C2Si(CH3)3–
C2H3, 260 (14); M+ −C2Si(CH3)3–3CH3, 242 (18).
Anal. Calc. for C21H33NSi3 (383.75): C, 65.73; H, 8.67.
Found: C, 65.61; H, 8.51%.
Yield: 2.4 g (6.3 mmol, 63%, rel. 3c). M.p. 69°C. IR
1
(NaCl, cm−1): wCꢁC=2160 (vs). H-NMR (CDCl3): l
0.79 (s, 3 H, SiCH3), 2.28 (s, 6 H, NCH3), 3.77 (s, 2 H,
CH2), 7.3–7.4 (m, 9 H, C6H4, C6H5), 7.5–7.6 (m, 4 H,
C6H4, C6H5), 8.3–8.4 (m, 1 H, C6H4). 13C{1H}-NMR
(CDCl3): l 1.9 (SiCH3), 44.7 (NCH3), 64.2 (CH2), 92.7
(SiCꢁC), 104.8 (SiCꢁC), 123.3, 126.7, 128.0, 128.1,
128.4, 129.9, 131.9, 132.6, 137.3, 146.4 (C6H4, C6H5).
29Si{1H}-NMR (CDCl3): l −50.6. EI MS m/e (rel.
3.10. Synthesis of [C6H4CH2N(CH3)2-2](H2CꢀCH)-
Si{NH[C6H2(CH3)3-2,4,6]}2 (10)
A total of 1.30 g (5.0 mmol) of [C6H4CH2N(CH3)2-
2](H2CꢀCH)SiCl2 (3d) dissolved in 50 ml of diethyl
ether are slowly added to a solution of 10.0 mmol
LiNH[C6H2(CH3)3-2,4,6] (obtained from the reaction of
int.): M+, 379 (41); M+ −CH3, 364 (32); M+
N(CH3)2, 335 (20); M+ −3CH3, 334 (24); M+
−
−
C2C6H5, 278 (29); M+ −C2C6H5–CH3, 263 (46);
4.0 ml 2.5 M BuLi in n-hexane and 1.35 g (10.0 mmol)
n
M
+ −C2C6H5–N(CH3)2, 234 (70); M+ −C2C6H5–
N(CH3)2–CH3, 219 (34); M+ −2C2C6H5, 177 (21);
NH2[C6H2(CH3)3-2,4,6] in 3.0 ml of diethyl ether) at
−70°C. The reaction mixture is warmed to 25°C for 12
h and then filtered through a pad of Celite. After
removal of all volatile materials at 25°C the orange
residue is crystallized from n-pentane at −30°C to
obtain compound 10 as orange crystals.
M
+ −2C2C6H5–CH3, 162 (19); SiC2C6H5+, 129 (21);
HC2C6H5+, 102 (17); C6H5CH2+, 91 (16); C6H5+, 77 (9);
CH2N(CH3)2+, 58 (100). Anal. Calc. for C26H25NSi
(379.58): C, 82.27; H, 6.64. Found: C, 81.92; H, 6.41%.
Yield: 2.0 g (4.37 mmol, 88%, rel. 3d). M.p. 172°C.
IR (KBr, cm−1): wNH=3175 (br); wCH=3044 (s), 3006
(m), 2978 (s), 2942 (vs), 2856 (s), 2818 (s), 2773 (s);
3.9.6. Data for
[C6H4CH2N(CH3)2-2](H2CꢀCH)Si(CꢁCC6H5)2 (9b)
Yield: 2.5 g (6.5 mmol, 65%, rel. 3d). B.p. 190°C/5×
10−2 mbar (ball tube distillation). IR (NaCl, cm−1):
wCH=3047 (s), 2947 (vs), 2850 (s), 2812 (s), 2773 (s);
1
wCꢀC=1594 (m). H-NMR (CDCl3): l 2.18 (s, 12 H,
o-CH3), 2.22 (s, 6 H, NCH3), 2.27 (s, 6 H, p-CH3), 3.38
(s, 2 H, CH2), 4.51 (br, 2 H, NH), 6.1–6.4 (m, 3 H,
C2H3), 6.81 (s, 4 H, C6H2), 7.1–7.2 (m, 1 H, C6H4),
7.2–7.4 (m, 2 H, C6H4), 7.8–8.0 (m, 1 H, C6H4).
13C{1H}-NMR (CDCl3): l 20.1 (o-CH3), 20.4 (p-CH3),
44.9 (NCH3), 64.7 (CH2), 126.6, 128.8, 128.9, 130.0,
130.3, 130.8, 135.6, 135.7, 135.8, 138.6, 140.7, 143.5
(C2H3, C6H2, C6H4). EI MS m/e (rel. int.): M+, 457
(8); M+ −N(CH3)2, 413 (8); M+ −C6H2(CH3)3, 338
(100). Anal. Calc. for C29H39N3Si (457.72): C, 76.09; H,
8.59. Found: C, 76.17; H, 8.76%.
1
wCꢁC=2156 (vs); wCꢀC=1588 (s). H-NMR (CDCl3): l
2.33 (s, 6 H, NCH3), 3.81 (s, 2 H, CH2), 6.2–6.3 (m, 2
H, C2H3), 6.4–6.5 (m, 1 H, C2H3), 7.2–7.5 (m, 9 H,
C6H4, C6H5), 7.5–7.7 (m, 4 H, C6H4, C6H5), 8.3–8.4
(m, 1 H, C6H4). 13C{1H}-NMR (CDCl3): l 44.7
(NCH3), 63.9 (CH2), 91.4 (SiCꢁC), 105.6 (SiCꢁC),
123.3, 126.8, 127.8, 128.2, 128.5, 130.1, 131.6, 131.8,
132.0, 133.7, 135.3, 146.4 (C2H3, C6H4, C6H5). EI MS
m/e (rel. int.): M+, 391 (13); M+ −CH3, 376 (11);
M
M
+ −C2H3, 364 (10); M+ −CH3–C2H3, 348 (19);
+ −C2C6H5, 290 (47); M+ −C2C6H5–N(CH3)2, 247
3.11. Synthesis of [C6H4CH2N(CH3)2-2](H2CꢀCH)
Si[P(C6H5)2]2 (11)
(100); HC2C6H5+, 102 (47); CH2N(CH3)2+, 58 (21).
Anal. Calc. for C27H25NSi (391.59): C, 82.82; H, 6.44.
Found: C, 82.82; H, 6.04%.
A solution of 2.9 g (15.4 mmol) PH(C6H5)2 in 50 ml
of THF is reacted with equimolar amounts of a 1.6 M
CH3Li solution in diethyl ether at −30°C. The reddish
colored reaction mixture is gently warmed to 25°C.
Afterwards it is added dropwise to a solution of 2.0 g
(7.7 mmol) of [C6H4CH2N(CH3)2-2](H2CꢀCH)SiCl2 (3d)
in 50 ml of THF. After warming overnight to 25°C the
solvents were removed under vacuum and the obtained
3.9.7. Data for
[C6H4CH2N(CH3)2-2](H2CꢀCH)Si[CꢁCSi(CH3)3]2 (9c)
Yield: 1.85 g (4.8 mmol, 48%, rel. 3d). B.p. 190°C/5×
10−2 mbar (ball tube distillation). IR (NaCl, cm−1):
wCH=3047 (s), 2953 (vs), 2893 (m), 2774 (s), 2721 (s),
1
2697 (s); wCꢁC=2105 (vw); wCꢀC=1587 (m). H-NMR

72
M. Weinmann et al. / Journal of Organometallic Chemistry 563 (1998) 61–72
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W. Malisch, New J. Chem. 13 (1989) 319. (b) H.H. Karsch, H.U.
Reisacher, B. Huber, G. Mu¨ller, W. Malisch, K. Jo¨rg, Angew.
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(1990) 349. (b) H. Lang, M. Leise, L. Zsolnai, M. Fritz, J.
Organomet. Chem. 395 (1990) C30. (d) H. Lang, M. Leise, J.
Organomet. Chem. 393 (1990) C17. (e) H. Lang, M. Leise, L.
Zsolnai, Polyhedron 11 (1992) 1281. (f) H. Lang, Phosphorus,
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brown slurry is treated with 100 ml of dichloromethane.
The suspension obtained is filtered through a pad of
Celite. After cooling to −30°C compound 11 is ob-
tained as an off-white solid.
Yield: 1.85 g (3.3 mmol, 43%, rel. 3d). M.p. 112°C.
IR (KBr, cm−1): wCꢀC=1593 (m). 1H-NMR (CDCl3): l
2.07 (s, 6 H, NCH3), 3.21 (s, 2 H, CH2), 5.81 (dd,
3
2JHH=3.2 Hz, JHH=19.8 Hz, 1 H, C2H3), 6.10 (dd,
2JHH=3.2 Hz, 3JHH=14.5 Hz, 1 H, C2H3), 6.3–6.5 (m,
1 H, C2H3), 7.1–7.7 (m, 24 H, C6H4, C6H5). 13C{1H}-
NMR (CDCl3): l 44.9 (NCH3), 63.6 (CH2), 125–138
(C2H3, C6H4, C6H5), 144.0 (C6H4). 29Si{1H}-NMR
1
(CDCl3): l −14.0 (t, JPSi=49.3 Hz). 31P{1H}-NMR
(CDCl3): l −58.5 (s). EI MS m/e (rel. int.): M+, 560
(56); M+ −CH3, 544 (7); M+ −P(C6H5)2, 374 (100);
P(C6H5)2, 185 (29). Anal. Calc. for C35H35NP2Si
(559.70): C, 75.11; H, 6.30. Found: C, 74.25; H, 6.40%.
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Acknowledgements
We are grateful to the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie for
financial support. We thank Th. Jannack for carrying
out the MS measurements as well as S. Ahrens and K.
Do¨rr for assistance in drawing up the manuscript.
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2
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.
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