2-(dimethylphosphinomethyl)- and 2-(methylthiomethyl)phenyl silicon compounds: Higher coordination with soft donors

Article abstract of DOI:10.1016/S0022-328X(02)02164-2

The synthesis of trimethoxy-, trifluoro-, trihydrido-, and hydrido(phenyl)chlorosilanes, and of hydrido(phenyl)silyltriflates bearing an additional 2-(dimethylphosphinomethyl)phenyl- or a 2-(methylthiomethyl)phenyl substituent is described. The coordinati

Full text of DOI:10.1016/S0022-328X(02)02164-2

Journal of Organometallic Chemistry 667 (2003) 167Á175
/
www.elsevier.com/locate/jorganchem
2-(Dimethylphosphinomethyl)- and 2-(methylthiomethyl)phenyl
silicon compounds: higher coordination with soft donors
U.H. Berlekamp, A. Mix, B. Neumann, H.-G. Stammler, P. Jutzi *
Faculty of Chemistry, Anorganische Chemie III, University of Bielefeld, Universitatsstraße 25; D-33615 Bielefeld, Germany
¨
Received 1 October 2002; received in revised form 27 November 2002; accepted 2 December 2002
Abstract
The synthesis of trimethoxy-, trifluoro-, trihydrido-, and hydrido(phenyl)chlorosilanes, and of hydrido(phenyl)silyltriflates
bearing an additional 2-(dimethylphosphinomethyl)phenyl- or a 2-(methylthiomethyl)phenyl substituent is described. The
coordination of the phosphorus and sulfur donor in the aryl side chain to the silicon center is discussed on the basis of NMR
spectroscopic investigations. The trimethoxy and trifluorosilanes do not show any coordination. Weak donorÁsilicon interactions
/
are found in the trihydrido- and in the hydrido(phenyl)chlorosilanes. The crystal structure of chloro-bis-[(2-(methylthiomethyl)phe-
nyl]silane (13) [Angew. Chem. 111 (1999) 2071] features a distorted tetrahedral geometry at silicon with an additional weak donor-
coordination. Different structural properties were found in the corresponding P- and S-donor functionalized phenylsilyl triflates.
The S-donor compound 15 features a covalent structure with pentacoordination and a trigonal-bipyramidal geometry at the silicon
atom. In the analogous P-donor derivative 14 the spectroscopic data indicate an ionic structure with a tetracoordinated silicon atom.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Silicon; 2-(Dimethylphosphinomethyl)phenylsilanes; 2-(Methylthiomethyl)phenylsilanes; 2-(Dimethylphosphinomethyl)phenylsilyl
triflate; 2-(Methylthiomethyl)phenylsilyl triflate; Si-pentacoordination; X-ray structure
1. Introduction
silicon compounds bearing additional phosphorus and
sulfur containing groups in order to study the potential
of these donors to induce higher coordination at silicon.
For this purpose we have synthesized exemplarily (2-
dimethyphosphinomethyl)phenyl- and (2-methylthio-
methyl)phenylsilicon compounds with further methoxy,
hydrido, halogeno, and triflate groups. In order to
elucidate structural parameters we investigated these
compounds by X-ray crystal structure analysis, NMR
and IR spectroscopic methods, and by conductivity
measurements. We compared the obtained data with
those of the analogous N- and O-donor functionalized
derivatives.
It is well known that the coordination sphere at
silicon in organosilicon compounds can be extended by
the formation of donorÁacceptor complexes [1]. A very
/
successful approach to induce higher coordination is the
integration of a donor into the side chain of an alkyl or
an aryl substituent. By the use of this strategy a lot of
higher coordinated neutral and cationic silicon com-
pounds including low-valent silicon species [2Á21] have
/
been synthesized. In contrast to the well investigated
amino-functionalized arylsilanes, only a few papers
report on corresponding silicon compounds in which
ether, thioether, and phoshino groups are intramolecu-
larly coordinated at silicon [6,19Á24]. In recent years, we
/
have investigated the coordination behavior of silicon
compounds bearing substituents with s- or p-donor
functions [6,23]. In this context, we are interested also in
2. Results and discussion
2.1. Syntheses
1-Bromo-2-(dimethylphosphinomethyl)benzene (1)
and 1-bromo-2-(methylthiomethyl)benzene (2) were
synthesized by standard procedures [24]. Lithiation
* Corresponding author. Tel.: ꢀ
106-6026.
E-mail address: peter.jutzi@uni-bielefield.de (P. Jutzi).
/
49-521-106-6181; fax: ꢀ49-521-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(02)02164-2

168
U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á175
/
was performed by reacting the bromo compounds 1 and
2 with n-butyllithium in hexane at low temperature. The
resulting suspensions of the aryl lithium compounds 3
and 4 were used directly without further purification
(Scheme 1).
Linkage of the side-chain functionalized aryl systems
3 and 4 to silicon was performed by reaction with
tetramethoxysilane which gave the aryltrimethoxysi-
lanes 5 and 6 in good yields as colorless viscous liquids
fairly stable to air and moisture. The P-donor functio-
nalized derivative 5 has been previously described by
in moderate yields. Both compounds were obtained as
moisture sensitive colorless oily liquids. The twofold S-
donor functionalized chlorosilane 13 [6] was synthesized
in good yields by reaction of 4 with trichlorosilane in a
2:1 stoichiometry and was obtained as a pale yellow
viscous oil very sensitive to air and moisture.
Treatment of the chlorosilanes 11 and 12 with
trimethylsilyl trifluoromethanesulfonate in hexane
yielded the P- and S-donor functionalized silyltriflates
14 and 15. Compound 14 was isolated in moderate
yields as a colorless powder. The corresponding triflate
15 was obtained as a colorless viscous oil. Both
derivatives are sensitive to air and moisture and
insoluble in non-polar solvents.
Muller at al. [22]. Treatment of 6 with one equivalent of
¨
the boron trifluoride diethylether complex gave the
trifluorosilane 8 in good yields as a colorless air sensitive
oily liquid. The corresponding reaction was performed
also with compound 5. After evaporation of all volatile
components in vacuo a pale yellow viscous oil remained
which consisted of the desired trifluorosilane 7 and of
some unidentified by-products, according to NMR
investigations. Attempts to purify 7 by distillation led
to decomposition.
2.2. X-ray crystal structures
2.2.1. Chloro-bis-[(2-methylthiomethyl)phenyl]silane
(13) [35]
Crystals of the chlorosilane 13 were grown from
hexane. 13 crystallizes in the space group P21/c. The
unit cell contains four crystallographically independent
molecules. The coordination geometry at silicon is
initially described here on the basis of a very distorted
trigonal-bipyramidal arrangement (see Fig. 1).
The axial positions are occupied by the sulfur atom
S(1) and the chloro substituent. The silicon sulfur S(1)
distance of 313.3 pm is considerably shorter than the
sum of the van der Waals radii of 390 pm [34]. This
indicates at least a weak silicon sulfur donor interaction.
We used the alkoxysilanes 5 and 6 also as substrates
for the synthesis of hydridosilanes. Thus, reduction of 5
and 6 with LiAlH4 gave the corresponding trihydrido-
silanes 9Á10. Both compounds were isolated as colorless
/
oily liquids in moderate yields. The S-donor functiona-
lized compound 10 hydrolyses slowly in the presence of
moisture. The P-donor functionalized derivative 9
ignites spontaneously when exposed to air.
Linkage of the side-chain functionalized aryl systems
to silicon was carried out also by reaction of the
aryllithium derivatives 3 and 4 with chlorosilanes.
Thus, reaction with one equivalent of phenyldichlorosi-
lane gave the corresponding arylchlorosilanes 11 and 12
In comparison to SiÃ
/
Cl bonds in tetra-coordinated
chlorosilanes [36], the SiÃ
/Cl bond in 13 is slightly
elongated to 217.6 pm. The positions of the axial atoms
deviate significantly from an ideal arrangement. The
Scheme 1.

U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á
/175
169
Fig. 1. ORTEP drawing of chloro-bis[2-(methylthiomethyl)phenyl]si-
lane (13). The ellipsoids are at the 50% level probability. Except H(1),
all hydrogen atoms are omitted for clarity. Selected bond lengths (pm)
Fig. 2. ORTEP drawing of 2-[(methylthiomethyl)phenyl]silyl trifluor-
omethanesulfonate (15). The ellipsoids are at the 50% level probability.
Except H(1), all hydrogen atoms are omitted for clarity. Selected bond
and angles (8): Si(1)Ã
145 (5); Si(1)ÃS(1) 313.30(16); Si(1)Ã
C(1) 112.60(17); C(9)ÃSi(1)ÃH(1) 116.4(18); C(1)Ã
114.7(18); C(9)ÃSi(1)ÃCl(1) 105.71(13); C(1)ÃSi(1)ÃCl(1) 104.57(13);
Cl(1)ÃSi(1)ÃH(1); 100.8(18); C(9)ÃSi(1)ÃS(1) 85.69(12); C(1)ÃSi(1)Ã
S(1) 76.32(12); S(1)ÃSi(1)ÃH(1) 67.5(18); Cl(1)ÃSi(1)ÃS(1) 166.76(6).
/
C(1) 187.4(4); Si(1)Ã
Cl(1) 217.60(14); C(9)Ã
Si(1)Ã
/
C(9) 186.6(4); Si(1)Ã
Si(1)Ã
H(1)
/
H(1)
/
/
/
/
/
/
/
/
lengths (pm) and angles (8): Si(1)Ã
185.96(14); Si(1)ÃH(1) 132.0 (17); Si(1)Ã
183.93(11); S(2)ÃO(1) 150.27(10); S(2)ÃO(2) 142.43(11); S(2)Ã
142.86(11); C(9)ÃSi(1)ÃC(1) 117.11(6); C(9)ÃSi(1)Ã
C(1)ÃSi(1)ÃH(1) 118.5(7); C(9)ÃSi(1)ÃO(1) 94.64(6); C(1)Ã
O(1) 96.06(5); O(1)ÃSi(1)ÃH(1); 93.8(8); C(9)ÃSi(1)ÃS(1) 88.32(4);
C(1)ÃSi(1)ÃS(1) 83.90(4); S(1)ÃSi(1)ÃH(1) 83.3(8); O(1)ÃSi(1)ÃS(1)
176.69(4).
/
C(1) 187.46(14); Si(1)Ã
/
C(9)
/
/
/
/
/
/
S(1) 259.54(5); Si(1)Ã
/
O(1)
/
/
/
/
/
/
/
/
/
O(3)
/
/
/
/
/
/
/
/H(1) 122.3(7);
/
/
/
/
/
Si(1)Ã
/
angle included by Cl(1), Si(1) and S(1) is reduced to
166.88. The hydrogen atom H(1) and the aryl substi-
tuents represented by C(1) and C(9) form the equatorial
plane of the trigonal-bipyramid. The silicon atom is
placed 40 pm outside of this plane in direction to the
chloro substituent. This deviation effects an increase of
the angles included by the axial chlorine atom, the
silicon atom, and the equatorial substituents. Simulta-
/
/
/
/
/
/
/
/
/
/
that found in 13 and in other sulfur-donor functiona-
lized silicon compounds and indicates a rather strong
interaction. Effected by the S-donor coordination, the
SiÃ
/
O bond in the silyl triflate unit is elongated to 183.93
neously, the angles C(1)Ã
/
Si(1)Ã
/
S(1), C(9)Ã
/
Si(1)Ã
/
S(1)
pm.
and H(1)ÃSi(1)ÃS(1) are decreased. The bond angles in
/
/
the equatorial plane range from 112.6 to 116.48 and
correspond more likely to values typical for a tetrahe-
dral geometry. As a result of the described structural
parameters for 13, the coordination geometry at silicon
might be better described as a distorted tetrahedron with
an additional weakly coordinating donor.
2.3. Coordination behavior
Intramolecular donor-coordination in these types of
silicon compounds should be identifiable by 29Si-NMR
spectroscopy. In comparison to the tetra-coordinated
analogues without donor function, the resonances of
type B compounds (Scheme 2) are expected to be shifted
towards higher-field at least to a small extend [2].
In contrast, the resonances of open-ring derivatives
(type A) should not differ significantly from those of the
parent compounds. Beside chemical shift values, the
coupling of silicon to adjacent nuclei should be sensitive
for geometric changes. We used chemical shift values
and coupling constants to assess the structure of the
novel P- and S-donor functionalized silicon derivatives
in solution. The important NMR spectroscopic data are
presented in Table 1. The corresponding data of the N-
and O-donor functionalized analogues are listed for
2.2.2. [(2-Methylthiomethyl)phenyl]silyl
trifluoromethanesulfonate (15) [35]
Crystals of compound 15 were obtained by storage of
the oily product at 5 8C. The compound crystallizes in
¯
space group P1: The unit cell contains two independent
/
molecules. The molecular structure of 15 is presented in
Fig. 2.
The central silicon atom is pentacoordinated in a
trigonal-bipyramidal fashion. The two phenyl substitu-
ents, represented by C(1) and C(9), and the hydrogen
atom H(1) span the equatorial plane. The sum of the
bond angles in the equartorial plane deviates with 357.98
only slightly from the ideal value of 3608. The silicon
hydrogen bond is found to be rather short compared
with other hydridosilanes. This reflects an enhanced s-
character in the SiÃ
/
H bond. The sulfur donor S(1) and
the oxygen atom O(1) of the triflate substituent occupy
the axial positions of the trigonal bipyramid. The
arrangement of S(1), Si(1) and O(1) is nearly linear.
The SÃ
/
Si distance of 259.45 pm is much shorter than
Scheme 2.

170
U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á175
/
Table 1
29Si-NMR data of N-, O-, P-, and S-donor functionalized arylsilicon compounds
a
PhNSi(OEt)3 [26]
a
PhOSi(OMe)3 [19]
a
PhPSi(OMe)3 (5) [22]
a
PhSSi(OMe)3 (6)
PhSi(OMe)3 [25]
57.5
d (29Si) (ppm)
ꢁ/
ꢁ
/
57.17
ꢁ
/
53.9
ꢁ
/
53.2
ꢁ
/
53.6
b
c
Dd (Si) (ppm)
ꢀ
/
0.59
ꢀ
/
3.6
ꢀ
/
4.3
ꢀ
/
3.9
PhSiF3 [25]
73.2
PhNSiF3 [27]
PhOSiF3 [19]
PhPSiF3 (7)
PhSSiF3 (8)
d (29Si) (ppm)
ꢁ/
ꢁ
/
101.5
ꢁ
/
88.0
ꢁ
/
72.0
ꢁ
/
71.9
a
Dd (Si) (ppm)
J(Si, F) (Hz)
ꢁ
/
28.3
ꢁ
/
14.8
ꢁ
/
1.3
ꢁ
/
1.2
268
PhSiH3 [25]
236
PhNSiH3 [28]
240
PhOSiH3 [19]
268
PhPSiH3 (9)
266
PhSSiH3 (10)
d (29Si) (ppm)
ꢁ
/
60.1
ꢁ
/
71.5
ꢁ
/
61.8
ꢁ
/
62.4
J(Si, P)ꢂ
Dd (Si) (ppm)
J(Si, H) (Hz)
/
5.6 Hz
ꢁ
/
65.0
a
ꢁ
/
11.4
ꢁ
/
1.7
ꢁ
/
2.3
ꢁ/4.9
200
Ph2SiHCl [25]
199
PhNSiPhHCl [3]
197
PhOSiPhHCl [29]
201
PhPSiPhHCl (11)
200
PhSSiPhHCl (12)
d (29Si) (ppm)
ꢁ
/
5.4
ꢁ
/
53.6
ꢁ
/
22.6
ꢁ
/
10.1
J(Si, P)ꢂ
Dd (Si) (ppm)
J(Si, H) (Hz)
/
7.5 Hz
ꢁ
/
12.4 Hz
a
ꢁ
/
48.2
ꢁ
/
17.2
ꢁ
/
5.3
ꢁ/7.0
236
Ph2SiHTrf d[30]
279
PhNSiPhHTrf [5]
264
PhOSiPhHTrf [19]
238
PhPSiPhHTrf (14)
251
PhSSiPhHTrf (15)
d (29Si) (ppm)
ꢁ
/
2.1
ꢁ
/
56.2
ꢁ
/
48.7
ꢁ
/
32.4
J(Si, P)ꢂ
Dd (Si) (ppm)
J(Si, H) (Hz)
/
40 Hz
ꢁ
/
42.8
a
ꢁ
/
54.1
ꢁ
/
46.6
ꢁ
/
30.3
ꢁ
/
40.7
257
290
286
258
281
a
PhN, (2-dimethylaminomethyl)phenyl; PhO, (2-methoxymethyl)phenyl; PhP, (2-dimethylphosphinomethyl)phenyl; PhS, (2-methylthio-
methyl)phenyl.
b
Shift difference to the analogous arylsilane without donor function.
In comparison with PhSi(OEt)3.
Trf, trifluoromethanesulfonate.
c
d
comparison. In the following, we discuss the coordina-
tion behavior in the respective classes of arylsilicon
compounds on the basis of the NMR data presented in
Table 1.
In the class of the aryl(trimethoxy)silanes, the reso-
nances of the P-donor and S-donor functionalized
compounds 5 [22] and 6 show no upfield shift in
comparison to phenyltrimethoxysilane and to the corre-
sponding N-donor functionalized species. Thus, a for-
show only minor upfield shifts in comparison to
phenylsilane. The Dd values of ꢁ2.3 (9) and ꢁ4.9
(10) give no clear evidence for the existence of higher
coordination at silicon. Also the 1J(Si, H) coupling
constants of 9 and 10 correspond to that of phenylsilane.
On the basis of these data, a non-coordinating behavior
is anticipated. However, for the P-donor derivative 9 a
/
/
small J(SiÃ
comparison of nJ(Si, P) coupling constants (nꢂ
[25], we exclude a 4J coupling via the aromatic ring and
attribute this coupling to a rather weak PÃSi interac-
tion. Due to the comparable d 29Si and J(Si, H) data
found for 9 and 10, we suppose a rather weak donorÁ
silicon interaction also for the S-donor compound 10.
The comparatively strongest donorÁsilicon interaction
/P) coupling of 5.6 Hz is observed. Based on a
/
1Á4)
/
mation of a donorÃ/acceptor bond can be excluded, and
compounds with structures of type A are present.
In the class of the aryl(trifluoro)silanes, the data of
the P- and S-donor containing compounds 7 and 8 give
no indication for a donor complexation. The observed
29Si resonances are nearly identical with that of phenyl-
trifluorosilane. Furthermore, the 1J(Si, F) coupling
constants do not differ markedly from that found in
the parent compound. In addition, no J(Si, P) coupling
is observed for compound 7. Thus, both compounds
obviously behave like tetracoordinated silanes and form
structures of type A. These results are in accordance
with recently published theoretical investigations con-
cerning the adduct formation behavior of SiF4. In
contrast to N- and O-donors, the tendency of P- and
S-donors to form adducts with SiF4 was found to be
negligibly small [31].
/
1
/
/
is presumably present in the N-donor functionalized
compound.
In the class of the chloro(aryl)(hydrido)phenylsilanes,
the 29Si resonances of the P- and S-donor containing
derivatives 11 and 12 are shifted towards higher-field in
comparison to that of chlorodiphenylsilane. Corre-
sponding to the small Dd values of ꢁ
7.0 ppm (12), compounds of type B (Scheme 2) with
weak donorÁsilicon interactions are present. Addition-
/5.3 (11) and
ꢁ
/
/
1
ally, a J(Si, P) coupling of 7.5 Hz is observed in the P-
1
donor functionalized silane 11. The J(Si, H) couplings
In the class of the aryl(trihydrido)silanes, the situation
is more complicated. The 29Si resonances of 9 and 10
of 11 and 12 show only minor differences in comparison
with that of the parent compound, in accord with only

U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á
/175
171
small changes in the hybridization of the respective
silicon atoms. The NMR data of 13 confirm that the
chelate structure of type B found in the solid state is also
present in solution. Thus, the 29Si resonance is shifted
towards higher-field by 12.8 ppm. In the 1H-NMR
spectrum the benzylic protons appear as AB system.
Only one set of signals is obtained for both aryl
substituents. This finding implies a dynamic coordina-
tion of the two S-donors in 13 similar to that observed
for other chlorosilanes with two donor groups [28]. The
1J(Si, H) coupling constant of 251 Hz corresponds to
that found for 12 and is considerably smaller than that
of the comparable N-donor functionalized compound
The 29Si resonance of the P-donor functionalized silyl
triflate 14 is also observed at higher-field but the shift
difference Dd for 14 (ꢁ
/
30.3 ppm) is smaller than in 15
Si) coupling of 40 Hz clearly
(ꢁ
/
42.8 ppm). A 1J(PÃ
/
indicates the existence of a silicon phosphorus bond.
The 31P resonance of 14 is shifted towards lower-field in
comparison to other (2-dimethylphospinomethylphe-
nyl)silanes presented in this paper and is observed at
ꢁ12.4 ppm. We attribute this shift to a significant
/
transfer of electron density from phosphorus to silicon.
In the 1H-NMR spectrum of 14, the benzylic protons in
14 remain chemically non-equivalent even at higher
temperatures and appear as an AB system, due to a
stereochemically rigid silicon center. The 1J(Si, H)
coupling constant of 258 Hz is significantly smaller
than that found for other donor-functionalized hydri-
dosilyl triflates and corresponds nearly to the value
found in diphenylsilyltriflate. This indicates an sp3-
hybridized silicon atom in this derivative. Based on the
NMR data of 14, we assume a structure of type D
(Scheme 3) with a tetracoordinated silicon center. The
charge distribution might be similar to that in the ionic
PhNSiPhHCl (1J(Si, H)ꢂ
bipyramidal structure and thus a strong donorÁ
interaction has been found [3].
/
279 Hz), for which a trigonal-
/silicon
Donor-functionalized silyl triflates are of special
interest with regard to their structure in the solid state
and in solution [5,19]. The 29Si resonance of the silyl
triflate 15 is observed at higher-field (Ddꢂ
/
ꢁ42.8 ppm)
/
in comparison to diphenylsilyl triflate, which indicates
higher coordination at silicon induced by a silicon S-
donor interaction [3,5,6,19]. Conclusions regarding the
geometry at the silicon atom in 15 can be drawn from
the coupling of the silicon atom to adjacent nuclei. The
1J(Si, H) coupling constant is significantly increased in
comparison to that of the parent compound. This
species Me(4ꢁn)P(SiMe3)nꢀ (nꢂ
/
1Á4) [37,38]. However,
/
dichloromethane solutions of 14 show no significant
conductivity. Obviously, compound 14 exists as a
contact ion pair. A comparable behavior in solution
has been described for P(SiMe3)4ꢀB(C6F5)4ꢁ [38].
reflects an enhanced s-character of the SiÃ
/
H bond [33]
1
due to a sp2 hybridization at silicon. Similar J(Si, H)
coupling constants have been observed for N- and O-
3. Conclusion
donor functionalized silyl triflates [3Á6,23]. According
/
to these data for 15, a structure of type C (Scheme 3)
with a trigonal-bipyramidal geometry at silicon compar-
able with that found in the solid state is also present in
solution. Although 15 contains two chiral centers which
should lead to the formation of diastereomers, only one
set of signals is obtained in the NMR spectra even at low
temperatures. Obviously, the energy barrier for the
Our results concerning the intramolecular coordina-
tion of P- and S-donor functionalized arylsilicon com-
pounds can be summarized as follows: In the
aryltrimethoxy- and aryltrifluorosilanes 5 and 6 there
is no evidence of a donorÁsilicon interaction. These
/
compounds behave like tetracoordinated silanes. In the
trihydridosilanes 9 and 10 the donor groups are
supposed to be weakly coordinating to silicon. A more
substantial donor silicon interaction is present in the
1
inversion at sulfur is small. In the H-NMR spectrum
below ꢁ10 8C (Tc) the benzylic protons appear as an
/
chlorosilanes 11Á12. However, according to small
/
AB system, while at higher temperatures only one singlet
is obtained. This finding indicates that the stereochemi-
cal rigidity at silicon is lifted either by a dynamic
Dd(29Si) values, the interaction is significantly weaker
than that in the N- and O-donor functionalized analo-
gues. The S-donor bond in the chlorosilane 13 effects a
distortion of the geometry at silicon in the solid state
and presumably also in solution. The structure in side-
chain functionalized (aryl)silyl triflates is obviously
determined by a subtile balance of charge distribution
between silicon and the donor atom. Thus, intramole-
coordination of the donor or by dissociationÁassocia-
/
tion of the triflate unit. The energy of activation for the
observed process can be determined to 12.5 kcal molꢁ1
[32,6].
cular donorÁsilicon interaction in the N-, O-, and S-
/
donor containing derivatives leads to pentacoordination
at silicon and formation of a type C structure (Scheme 3)
with a trigonal-bipyramidal geometry at the silicon
atom. In the corresponding P-donor compound the
spectroscopic data imply the existence of an ionic
Scheme 3.

172
U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á175
/
2
structure of type D with a tetrahedral geometry at the
silicon atom.
1H-NMR (CDCl3): 1.02 (d, J(P, H)ꢂ
CH3), 2.96 (s, 2H, ÃCH2Ã), 3.60 (s, 9H, Ã
(pseudo-t, 1H, ArÃH), 7.25 (d, J(H, H)ꢂ
ArÃH), 7.33 (pseudo-t, 1H, ArÃ
H), 7.65 (d, 3J(H, H)ꢂ
7.5 Hz, 1H, ArÃ
H); 13C{1H}-NMR (CDCl3): 13.6
(ꢁCH3), 38.8 (ÃCH2Ã), 50.2 (ÃOCH3), 124.6, 127.7,
127.9, 136.3, 145.3 (C-arom); 31P-NMR (CDCl3):
39.9; 29Si-NMR (CDCl3): ꢁ
53.2; MS m/z (relative
/
3.0 Hz, 6H,
OCH3), 7.15
8.6 Hz, 1H,
Ã
/
/
/
/
3
/
/
/
/
/
4. Experimental
/
/
/
/
/
All manipulations were performed under a dry argon
atmosphere using standard Schlenck techniques or a
nitrogen fitted glovebox. Solvents were dried by stan-
dard methods and distilled prior to use. NMR spectra
were recorded on a Bruker DRX 500 spectrometer
operated at 500 MHz for 1H, 470.6 MHz for 19F,
202.5 MHz for 31P, 125.7 MHz for 13C and 99.3 MHz
for 29Si at ambient temperature unless otherwise noted.
1H and 13C chemical shifts were referenced to residual
solvent resonances, 31P chemical shifts to external 85%
aqueous solution of H3PO4, 19F chemical shifts to
external CFCl3, and 29Si chemical shifts to external
Me4Si. All shifts are given in ppm. Mass spectra were
recorded on a VG Autospec instrument at 70 eV EI, 200
mA emission unless otherwise noted. IR Spectra were
recorded on a Bruker Vector 22 FTIR spectrometer.
ꢁ
/
/
intensity (%)): 272 (55), 181 (100); C12H21O3PSi
(272.36), Anal. Calc. C, 52.92; H, 7.77. Found: C,
52.58; H, 8.12%.
4.2.2. Trimethoxy-[2-(methylthiomethyl)penyl]silane
(6)
Colorless oil, yield: 25.3 mmol (6.54 g, 25%); b.p.
68 8C (0.02 mbar).
1H-NMR (CDCl3): 2.02 (s, 3H, Ã
/
CH3), 3.61 (s, 9H,
), 7.24 (pseudo-t, 1H, ArÃ
H), 7.68 (d, 3J(H, H)ꢂ
7.5 Hz, 1H,
H); 13C{1H}-NMR (CDCl3): 15.1 (Ã
CH3), 38.3
CH2Ã), 50.7 (ÃOCH3), 126.1, 128.8, 129.5, 136.5,
145.0 (C-arom); 29Si{1H}-NMR (CDCl3): ꢁ
53.6; MS
Ã
/
OCH3), 3.88 (s, 2H, Ã
H), 7.41 (m, 2H, ArÃ
ArÃ
(Ã
/
CH2Ã
/
/
/
/
/
/
/
/
/
/
Wave numbers (/
n˜) are given in cmꢁ1. Conductivity
m/z (relative intensity (%)): 258 (1), 226 (51), 211 (100),
181 (91), 151 (27), 121 (38), 105 (41), 91 (67), 84 (28), 59
(38), 45 (24); C11H18SSi (258.42), Anal. Calc. C, 51.12;
H, 7.02. Found: C, 53.44; H, 6.67% [39].
measurements of the silyl triflates were carried out in
CH2Cl2 solution at various concentrations. Elemental
analyses were performed by the microanalytical labora-
tory of the University of Bielefeld or by the Mikroana-
lytisches Labor Beller, Gottingen. The X-ray structural
¨
data were collected on a Nonius KappaCCD instru-
ment.
4.3. Synthesis of the aryltrifluorosilanes (general
procedure)
At 0 8C 10.6 mmol (2.66 ml) of the borontrifluoride
diethylether complex are added dropwise to a solution
of 10 mmol of the corresponding aryltrimethoxysilane in
20 ml diethylether. The cooling bath is removed and the
mixture is stirred for 20 h. All volatile components are
removed in vacuo.
4.1. Synthesis of the aryllithium compounds 3 and 4
A 1.6 m solution of n-butyllithium (62.5 ml) in hexane
(100 mmol) is slowly added at ꢁ50 8C to 100 mmol of
/
the corresponding arylbromide (1 or 2) solved in 50 ml
hexane or Et2O. The mixture is allowed to warm to
room temperature (r.t.) and stirred for additional 4 h.
The resulting suspensions of the aryllithium compounds
3 and 4 are used without further purification.
4.3.1. Trifluoro-[2-(dimethylphosphinomethyl)-
phenyl]silane (6)
Compound 6 was isolated together with by-products.
A purification failed, due to its sensitivity. Accordingly,
1
4.2. Synthesis of the aryltrimethoxysilanes (general
procedure)
a correct assignment of H- and 13C-NMR resonances
was not possible. Identification was performed by 29Si-
NMR.
1
A solution of 100 mmol of the aryllithium compound
29Si-NMR (CDCl3): ꢁ
/
72.0 (q, J(Si, F)ꢂ
/268 Hz).
3 or 4 is added dropwise at ꢁ50 8C to a solution of 18.3
/
g (100 mmol) of tetramethoxysilane in Et2O. The
mixture is warmed to r.t. After stirring for 20 h all
volatile components are removed in vacuo, and hexane
is added to the residue. After filtration the solvent is
removed and the oily residue is purified by distillation.
4.3.2. Trifluoro-[2-(methylthiomethyl)phenyl]silane (7)
The crude was purified by distillation. Colorless oil,
yield: 6.10 mmol (1.37 g, 65%), b.p. 30 8C (0.2 mbar).
1H-NMR (CDCl3): 1.94 (s, 3H, Ã
/
CH3), 3.78 (s, 2H,
7.5 Hz, 1H ArÃH), 7.41 (d,
H, 7.53 (t, J(H, H)ꢂ7.6
H, 7.77 (d, 3J(H, H)ꢂ
7.5 Hz, 1H, ArÃH);
13C-NMR (CDCl3): 14.6 (Ã
CH3), 38.6 (ÃCH2Ã), 127.0
Ã
/
CH2Ã
3J(H, H)ꢂ
Hz, 1H, ArÃ
/
), 7.35 (t, 3J(H, H)ꢂ
7.7 Hz, 1H, ArÃ
/
/
3
/
/
/
4.2.1. Trimethoxy-[2-(dimethylphosphinomethyl)-
penyl]silane (5)
Colorless oil; yield 62.0 mmol (16.9 g, 62%); b.p.
86 8C (0.02 mbar).
/
/
/
/
/
/
(C-arom), 128.4 (C-arom), 130.2 (C-arom), 133.1 (C-
arom), 136.6 (C-arom), 145.8 (C-arom); 19F-NMR

U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á
/175
173
1
71.9 (q, J(Si,
(CDCl3): ꢁ
/
85.7; 29Si-NMR (CDCl3): ꢁ
/
removed in vacuo, and hexane is added to the residue.
After filtration and evaporation of the solvent the
residue is purified by distillation.
F)ꢂ265 Hz); MS m/z (relative intensity(%)): 222 (27),
/
207 (4), 175 (100), 146 (15), 138 (16, 105 (6), 84 (7), 65
(33), 45 (20), 39 (18); C8H9F3SSi (222.30): Anal. Calc. C,
43.22; H, 4.08. Found: C, 43.27; H, 3.87%.
4.5.1. Chloro-[2-(dimethylphosphinomethyl)-
phenyl]phenylsilane (11)
Colorless oil; yield: 58.0 mmol (17.0 g, 51%); b.p.
4.4. Synthesis of the aryltrihydridosilanes (general
procedure)
145 8C (0.02 mbar).
2
1H-NMR (C6D6): 0.69 (d, J(P, H)ꢂ
/
26.7 Hz, 6H,
13.4 Hz, 2H,
H), 6.98 (t, 3J(H, H)ꢂ
7.4 Hz,
7.15 (m, 5H, ArÃH), 7.66Á7.67 (d,
7.3 Hz, 2H, ArÃH); 8.74 (d, J(H, H)ꢂ7.4
Hz, 1H, ArÃ
H); 13C-NMR (C6D6): 13.4 (d, J(C, P)ꢂ
2
At 0 8C a solution of 10 mmol of the corresponding
trimethoxysilane in 10 ml of Et2O is added slowly to a
suspension of 30 mmol (1.14 g) of LiAlH4 in 40 ml of
Et2O. After warming to r.t. and stirring for 20 h the
solvent is removed in vacuo, and hexane is added to the
residue. The mixture is filtered and after removing the
solvent in vacuo the crude product is purified by
distillation.
Ã
/
CH3), 2.58, 2.82 (AB-system, J(H, H)ꢂ
CH2Ã), 6.20 (s, 1H, SiÃ
1H, ArÃH), 7.07Á
3J(H, H)ꢂ
/
Ã
/
/
/
/
/
/
/
/
3
/
/
/
1
/
/
1
Hz), 39.6 (d, J(C, P)ꢂHz), 125.6 (C-arom), 128.4 (C-
/
arom), 129.8 (C-arom), 130.9 (C-arom), 131.3 (C-arom),
133.2 (C-arom), 134.5 (C-arom), 136.8 (C-arom), 145.6
(C-arom); 29Si-NMR (C6D6): ꢁ
/
10.1 (1J(SiÃ
/
H)ꢂ
7.5 Hz); 31P-NMR (C6D6): ꢁ
39.0; IR
H); Anal. Calc. for C15H18ClPSi
/
238
4.4.1. [2-Dimethylphosphinomethyl)phenyl]silane (9)
Colorless oil; yield: 4.9 mmol (0.89 g, 49%); b.p. 72 8C
(1 mbar).
Hz, 1J(Si, P)ꢂ
/
/
(liquid, CsI): 2177 (SiÃ
/
(292.82): C, 61.53; H, 6.19. Found: C, 61.53; H, 6.19%.
1H-NMR (CDCl3): 1.06 (s, 6H, Ã
CH2Ã), 4.30 (s, 3H, SiH3), 7.18Á
/
CH3); 2.89 (s, 2H,
Ã
/
/
/
7.20 (m, 2H, ArÃH);
/
4.5.2. Chloro-[2-(methylthiomethyl)phenyl]phenylsilane
(12)
Colorless oil; yield: 38.0 mmol (9.98 g, 38%); b.p.
3
3
7.36 (t, J(H, H)ꢂ
H)ꢂ7.5 Hz, 1H, ArÃ
(ÃCH3), 39.9 (ÃCH2Ã), 125.1 (C-arom), 127.6 (C-
arom), 128.2 (C-arom), 130.0 (C-arom), 137.4 (C-
arom), 144.8 (C-arom); 31P-NMR (CDCl3): ꢁ
41.3;
29Si-NMR (CDCl3): ꢁ62.4 (1J(Si, H)ꢂ
200.7 Hz,
1J(Si, P)ꢂ
5.6 Hz), MS CI, m/z (relative intensity
(%)): 181 (100), 121 (21), 117 (13), 105 (12), 91 (22);
IR (liquid, CsI): 2155 (SiÃH).
/
7.5 Hz, 1H, ArÃ
/
H), 7.60 (d, J(H,
/
/
H); 13C-NMR (CDCl3): 13.5
/
/
/
130 8C (0.02 mbar).
1H-NMR (C6D6): 2.54 (s, 3H, Ã
/
CH3), 3.89, 3.98 (AB-
12.1 Hz, 2H, ÃCH2Ã), 6.14 (s, 1H,
7.14 (m, 6H, ArÃH), 7.61 (m, 2H, ArÃH),
7.87 (d, 3J(H, H)ꢂ H); 13C-NMR
7.3 Hz, 1H, ArÃ
(C6D6): 14.3 (ÃCH3), 38.6 (ÃCH2Ã), 127.1 (C-arom),
2
/
system, J(H, H)ꢂ
/
/
/
/
/
SiH), 6.98Á
/
/
/
/
/
/
/
/
/
/
128.3 (C-arom), 128.4 (C-arom), 129.7 (C-arom), 130.0
(C-arom), 130.3 (C-arom), 131.7 (C-arom), 136.0 (C-
arom), 144.9 (C-arom); 29Si-NMR (C6D6): ꢁ
4.4.2. [2-(Methylthiomethyl)phenyl]silane (10)
Colorless oil; yield: 6.80 mmol (1.14 g, 67%); b.p.
83 8C (2 mbar).
/
12.4
(1J(SiÃ
Anal. Calc. for C14H15ClSSi (278.88): C, 60.30; H, 5.42.
Found: C, 60.95; H, 5.74%.
/
H)ꢂ
/
251 Hz); IR (liquid, CsI): 2181 (SiÃH);
/
1H-NMR (CDCl3): 1.97 (s, 3H, Ã
/CH3), 3.77 (s, 2H,
Ã
/
CH2Ã
/
), 4.26 (s, 3H, SiH3), 7.23Á
/
7.30 (m, 2H, ArÃH),
/
3
3
7.35 (t, J(H, H)ꢂ
H)ꢂ7.4 Hz, 1H, ArÃ
(ÃCH3), 39.2 (ÃCH2Ã), 127.7 (C-arom), 128.3 (C-
arom), 129.5 (C-arom), 130.9 (C-arom), 137.9 (C-
arom), 144.4 (C-arom); 29Si-NMR (CDCl3): ꢁ
65.0
1J(Si, H)ꢂ
200 Hz); MS m/z (relative intensity (%)):
167 (100), 121 (77), 105 (68), 91 (70), 77 (13), 65 (12), 53
H); Anal. Calc.
/
7.3 Hz, 1H, ArÃ
/
H), 7.61 (d, J(H,
4.5.3. Chloro-bis[2-(methylthiomethyl)phenyl]silane
(13)
/
/
H); 13C-NMR (CDCl3): 14.7
/
/
/
At ꢁ78 8C a solution of 100 mmol of in 100 ml of
/
Et2O is added slowly to a solution of 51 mmol (5.16 ml)
of trichlorosilane in 120 ml of Et2O. The mixture is
warmed to r.t. and is stirred for 20 h. The solvent is
removed in vacuo and hexane is added to the residue.
After filtration and evaporation of the solvent the
product is purified by distillation. Compound 14 is
isolated as a pale yellow oil. Yield: 34.2 mmol (11.6 g,
68%); b.p. 184 8C (0.02 mbar).
/
/
(13), 45 (11); IR (liquid, CsI):2157 (SiÃ
/
for C8H12SSi C, 57.39; H, 7.19. Found: C. 57.08; H
7.44%.
4.5. Synthesis of the arylphenylchlorosilanes (general
procedure)
1H-NMR (C6D6): 1.52 (s, 6H, Ã
/
CH3), 3.60, 3.68 (AB-
2
system, J(H,H)ꢂ
/
13.6 Hz, 4H, Ã
H), 7.07Á
7.4 Hz, 2H, ArÃ
CH3), 38.8 (ÃCH2Ã
129.0 (C-arom.), 130.0 (C-arom), 132.8 (C-arom), 136.6
(C-arom), 144.5 (C-arom); 29Si-NMR (C6D6): ꢁ
18.2
/
CH2Ã
/
), 6.39 (s, 1H,
SiH), 6.97Á7.00 (m, 2H, ArÃ
/
/
/
7.08 (m, 4H, ArÃ
/
3
At ꢁ
/
78 8C a solution of 100 mmol of in 100 ml of
H), 7.80 (d, J(H,H)ꢂ
/
/
H); 13C-NMR
Et2O is added slowly to a solution of 102 mmol (7.46 ml)
of phenylchlorosilane in 120 ml of Et2O. The mixture is
warmed to r.t. and is stirred for 20 h. The solvent is
(C6D6): 4.7 (Ã
/
/
/), 127.0 (C-arom.),
/

174
U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á175
/
(1J(SiÃ
/
H)ꢂ
/
251 Hz); IR (liquid, CsI): 2189 (SiÃ
/
H);
References
Anal. Calc. for C16H19ClS2Si (238.00): C, 56.68; H, 5.64.
Found: C, 56.57; H, 6.17%.
[1] First report concerning adduct formation: J.L. Gay-Lussac, L.J.
Thenard, Mem. Phys. Chem. Soc. 2 (1803) 317.
[2] Reviews: (a) R.J.P. Corriu, C. Guerin, J. Organomet. Chem. 198
(1980) 231. (b) R.J.P. Corriu, C. Guerin, Adv. Organomet. Chem.
20 (1982) 265. (c) C. Chuit, R.J.P. Corriu, C. Reye´, J.C. Young,
Chem. Rev. 93 (1993) 1371. (d) R.J.P. Corriu, J.C. Young, in: S.
Patai, Z. Rappoport, (Eds.) The Chemistry of Organic Silicon
Compounds, Wiley, New York, 1989, p. 1241. (e) D. Kost, I.
Kalikhman, in: Z. Rappoport, Y. Apeloig (Eds.), The Chemistry
of Organic Silicon Compounds, vol. 2, Wiley, Chichester, New
York, Weinheim, Brisbane, Singapore, Toronto, 1998, p. 1436.
[3] C. Chuit, R.J.P. Corriu, A. Mehdi, C. Reye´, Angew. Chem. 105
(1993) 1372.
4.5.4. [2-(Dimethylphosphinomethyl)phenyl]phenylsilyl
trifluoromethanesulfonate (14)
Thirteen millimole of trimethylsilyl triflate are added
slowly to a solution of 13 mmol (3.80 g) of the
chlorosilane 11 in 30 ml of hexane at ꢁ78 8C. The
/
mixture is allowed to warm slowly to r.t., and is stirred
for 20 h. The liquid layer is removed. The colorless solid
precipitate is washed three times with 25 ml of hexane
and dried in vacuo. The product is isolated as a colorless
powder. Yield: 6.40 mmol (2.60 g, 49%).
[4] F. Carre´, C. Chuit, R.J.P. Corriu, A. Mehdi, C. Reye´, Angew.
Chem. 106 (1994) 1152.
[5] J. Belzner, D. Shar, B.O. Kneisel, R. Herbst-Irmer, Organome-
¨
1H-NMR (CD2Cl2):1.73 (s, 3H, Ã
/
CH3), 1.78 (s, 3H,
CH3), 3.63, 3.65 (AB system, J(H, H)ꢂ14.3 Hz, 2H,
32.6 Hz, 1H, SiH), 7.44Á
7.57 (m, 1H, ArÃH), 7.59Á
H), 7.85 (d, 1J(H,H)ꢂ
7.4 Hz, 1H ArÃ
H); 13C-NMR (CD2Cl2): 15.7 (Ã
CH3), 16.0 (ÃCH3),
31.8 (d, 1J(P,C)ꢂ
36.9 Hz, ÃCH2), 120.8 (q, CF3), 126.0
(C-arom), 126.1 (C-arom), 129.1 (C-arom), 129.3 (C-
tallics 14 (1995) 1840.
2
Ã
/
/
[6] U.-H. Berlekamp, P. Jutzi, A. Mix, B. Neumann, H.-G. Stamm-
ler, W.W. Schoeller, Angew. Chem. 111 (1999) 2071.
[7] V. Kingston, B. Gostevskii, I. Kalikhman, D. Kost, J. Chem. Soc.
Chem. Commun. (2001) 1272.
2
Ã
/
CH2Ã
7.48 (m, 4H, ArÃ
7.61 (m, 3H, ArÃ
/
), 5.78 (d, J(P, H)ꢂ
/
/
/
H), 7.52Á
/
/
/
/
/
/
[8] I. Kalikhman, V. Kingston, B. Gostevskii, V. Pestunovich, D.
Stahlke, B. Walfort, D. Kost, Organometallics 21 (2002) 4468.
[9] I. Kalikhman, B. Gostevskii, O. Girshberg, S. Krivonos, D. Kost,
Organometallics 21 (2002) 2551.
/
/
/
/
2
[10] D. Kost, V. Kingston, B. Gostevskii, A. Ellern, D. Stahlke, B.
Walfort, I. Kalikhman, Organometallics 21 (2002) 2293.
[11] I. Kalikhman, S. Krivonos, L. Lameyer, D. Stahlke, D. Kost,
Organometallics 2 (2001) 1053.
arom), 129.7 (d, J(C, P)ꢂ
arom), 132.2 (C-arom), 135.0 (C-arom), 136.6 (C-arom),
143.1 (C-arom); 29Si-NMR (CD2Cl2): ꢁ32.4 (1J(Si,
H)ꢂ
257.5 Hz, 1J(Si, P)ꢂ40 Hz); 19F-NMR
(CD2Cl2): 131.3; 31P-NMR (CD2Cl2): ꢁ
12.4; IR (CsI):
H); Anal. Calc. for C16H18F3PSSi (406.44):
/
12 Hz, C-arom), 131.2 (C-
/
/
/
[12] P. Arya, J. Boyer, F. Carre´, R. Corriu, G. Lanneau, J. Lapasset,
M. Perrot, C. Priou, Angew. Chem. 101 (1989) 1069.
[13] R. Corriu, G. Lanneau, C. Priou, Angew. Chem. 103 (1991) 1153.
[14] H. Handwerker, C. Leis, R. Probst, P. Bissinger, A. Grohmann,
/
2144.9 (SiÃ
/
C, 47.28; H, 4.46. Found: C, 47.16; H, 4.77%.
P. Kiprof, E. Herdtweck, J. Blumel, N. Auner, C. Zybill,
¨
Organometallics 12 (1993) 2162.
[15] R. Probst, C. Leis, S. Gamper, E. Herdtweck, C. Zybill, N.
Auner, Angew. Chem. 103 (1991) 1155.
4.5.5. [2-(Methylthiomethyl)phenyl]phenylsilyl
trifluoromethanesulfonate (15)
[16] R.J.P. Corriu, B.S.P. Chauhan, G.F. Lanneau, Organometallics
14 (1995) 1646.
Seven millimole (1.25 ml) of trimethylsilyl triflate are
added slowly to a solution of 6.95 mmol (2.37 g) of the
chlorosilane 12 in 20 ml of hexane. The mixture is stirred
for 7 days. All volatile components are removed in
vacuo. The product is isolated as a colorless oil
contaminated with a small amount of the chlorosilane
[17] B.S.P. Chauhan, R.J.P. Corriu, G.F. Lanneau, C. Priou, N.
Auner, H. Handwerker, E. Herdtweck, Organometallics 14 (1995)
1547.
[18] R.J.P. Corriu, B.P.S. Chauhan, G.F. Lanneau, Organometallics
14 (1995) 4014.
[19] A. Mix, U.H. Berlekamp, H.-G. Stammler, B. Neumann, P. Jutzi,
J. Organomet. Chem. 521 (1996) 177.
1
12. Yield: 6.73 mmol (2.86 g, 90%; H-NMR).
[20] A. Chandrasekaran, R.O. Day, R.R. Holmes, Organometallics 15
(1996) 3189.
1H-NMR (CD2Cl2): 1.57 (s, 3H, Ã
/
CH3), 3.84 (br, 2H,
1
Ã
/
CH2Ã
1H, ArÃ
Hz, 1H, ArÃ
H)ꢂ6.5 Hz, ArÃ
ArÃ
(ÃCH2Ã
/
), 6.01 (s, 1H, SiH), 7.33 (d, J(H, H)ꢂ
H), 7.42 (m, 2H, ArÃ
H), 7.45 (t, 1J(H, H)ꢂ
H), 7.50 (m, 2H, ArÃ
/
6.0 Hz,
[21] R.-M.L. Mercado, A. Chandrasekaran, R.O. Day, R.R. Holmes,
Organometallics 18 (1999) 906.
/
/
/7.2
1
/
/
H), 7.63 (d, J(H,
[22] G. Muller, M. Waldkirch, A. Pape, in: N. Auner, J. Weis (Eds.),
¨
Organosilicon Chemistry III, Wiley-VCH, Weinheim, Berlin, New
York, 1998, p. 452.
1
/
/
H), 8.12 (d, J(H, H)ꢂ6.4 Hz, 1H
/
/
H); 13C-NMR (CD2Cl2): 14.8 (Ã
/CH3), 39.3
[23] (a) P. Jutzi, E.A. Bunte, Angew. Chem. 104 (1992) 1636;
(b) P. Jutzi, E.A. Bunte, Angew. Chem. Int. Ed. Engl. 31 (1992)
1605.
1
/
/
), 119.0 (q, J(C, F)ꢂ
/
318 Hz, CF3), 128.1 (C-
arom), 128.4 (C-arom), 128.6 (C-arom), 129.3 (C-arom),
130.8 (C-arom), 131.7 (C-arom), 133.0 (C-arom), 133.3
(C-arom.), 137.9 (C-arom), 144.7 (C-arom); 29Si-NMR
[24] G. Muller, M. Waldkirch, M. Winkler, Z. Naturforsch. Teil. B 49
¨
(1994) 106.
1
(CD2Cl2): ꢁ
/
42.8 (1J(Si, H)ꢂ
281 Hz); IR (KBr): 2192.1
/
[25] (a) J(Si, P) couplings in silylsubstituted dimethylphosphanes are
22 Hz; 2J(Si, P) couplings are in the range of 5Á
10
typically of 20Á
/
/
(SiÃH).
/
Hz, while 3J(Si, P) couplings are observable only in compounds
with very special geometric conditions [see 22b].;
Due to the oily consistence it was not possible to
purify the compound in order to obtain a correct CH
analysis.
(b) H. Marsmann, in: P. Diehl, E. Fluck, R. Kosfeld (Eds.), NMR
Principles and Progress, Springer-Verlag, New York, 1981, p. 65.

U.H. Berlekamp et al. / Journal of Organometallic Chemistry 667 (2003) 167Á
/175
175
˚
˚
[26] J. Boyer, C. Brelie`re, F. Carre´, R.J.P. Corriu, A. Kpoton, M.
Poirier, G. Royo, J.C. Young, J. Chem. Soc. Dalton Trans. (1989)
43.
molꢁ1
10.4500(2) A, aꢂ
,
triclinic, aꢂ
/
9.9320(2) A, bꢂ
78.505(1)8, bꢂ68.680(1)8, gꢂ
853.91(3) A ; Tꢂ100 K, space group P
chromated MoÁKa radiation (lꢂ0.71073), Zꢂ
cm3, F(000)ꢂ 0.423 mmꢁ1, crystal size: 0.09ꢃ
404, mꢂ
mm3, U range for data collection 3.06Á
30.008, 30 612 reflections
collected, 4960 unique (Rint 0.041), RFꢂ0.0356 for 4147 reflec-
0.0988 for all data, largest difference
/
10.0160(2) A, cꢂ
/
˚
˚
/
/
/
61.913(1) A,
1; graphite mono
2, Dcalc 1.526
0.2ꢃ0.3
3
˚
¯
/
Vꢂ
/
/
[27] R.J.P. Corriu, A. Kpoton, M. Porier, G. Royo, A. de Saxce, J.C.
Young, J. Organomet. Chem. 395 (1990) 1.
/
/
/
ꢂ
/
/
/
/
/
[28] N. Auner, R. Probst, F. Hahn, E. Herdtweck, J. Organomet.
Chem. 459 (1993) 25.
[29] U. Berlekamp, Dissertation, Universitat Bielefeld, 1999.
/
ꢂ
ꢂ/
/
/
¨
tions with I ꢀ
/
2sI, wRF2
˚
[30] W. Uhlig, Chem. Ber. 125 (1992) 47.
peak 0.524 e Aꢁ3. Crystallographic data for the structural
analyses of 13 and 15 have been deposited with the Cambridge
Crystallographic Data Centre, CCDC Nos. 184572 and 184573.
Copies of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
[31] W.W. Schoeller, A. Rozhenko, Eur. J. Inorg. Chem. (2000) 375.
[32] H. Friebolin, Basic One- and Two-Dimensional NMR Spectro-
scopy, 3rd ed, Wiley-VCH, Weinheim, New York, Chichester,
1998, p. 308ff.
[33] R.J.P. Corriu, M. Henner, J. Organomet. Chem. 74 (1974) 1.
[34] A.J. Bondi, J. Phys. Chem. 68 (1964) 441.
(fax: ꢀ
http://www.ccdc.cam.ac.uk).
[36] SiÃCl bonds are usually in the range of 201Á204 pm: W.S.
/
44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
[35] Crystallographic data of 13: C16H19ClS2Si, Mꢂ
/
338.97 g molꢁ1
˚
16.0490(8) A,
,
/
/
˚
˚
Monoclinic, aꢂ
bꢂ115.6480(10)8, Vꢂ
P21/c, graphite mono chromated MoÁ
0.71073), Zꢂ4, Dcalc
1.3098 cm3, F(0,0,0)ꢂ
mmꢁ1, crystal size: 0.2ꢃ 0.5 mm3, U range for data
0.4ꢃ
collection 3.25Á27.178, 14 658 reflections collected, 3712 unique
(Rint 0.0386), RFꢂ0.068 for 3712 reflections with I ꢀ2sI,
wRF2
0.2093 for all data, largest difference peak 1.528 e Aꢁ3).
Crystallographic data of 15: C15H15F3O3S2Si, Mꢂ392.48 g
/
13.9149(7) A, bꢂ
/
8.5451(4) A, cꢂ
/
3
Sheldrick, in: S. Patai, Z. Rappoport (Eds.), The Chemistry of
˚
/
/
1720.27(15) A ; Tꢂ
Ka radiation (lꢂ
712, mꢂ0.523
/183 K, space group
Organic Silicon Compounds, Wiley, New York, 1989, p. 236.
[37] H. Schafer, A.G. MacDiamid, Inorg. Chem. 15 (1976) 848.
¨
/
/
/
ꢂ/
/
/
[38] M. Driess, R. Barmeyer, C. Monse´, K. Merz, Angew. Chem. 113
(2001) 2366.
/
/
/
[39] In the reaction always a small amount of the corresponding silane
containing two donor-functionalized aryl substituents is formed
which can not be completely separated by distillation.
ꢂ/
/
/
˚
ꢂ/
/