N-bonded monosilanols: Synthesis and characterization of ArN(SiMe 3) SiMe2Cl and ArN(SiMe3)SiMe2OH (Ar = C6H5, 2,6-Me2C6H3, 2,6-iPr2C6H3)

Article abstract of DOI:10.1002/ejic.200401013

By the use of aniline and the sterically hindered aromatic primary amines, 2,6-Me₂C₆H₃NH₂ and 2,6-iPr ₂C₆H₃NH₂, N-bonded monochlorosilanes, ArN(SiMe₃)SiMe₂Cl [Ar = C ₆H₅ (1a), Ar = 2,6-Me₂C₆H ₃ (1b) and Ar = 2,6-iPr₂C₆H₃ (1c)] have been prepared by a sequential deprotonation at the nitrogen followed by reaction with silyl chlorides. Hydrolysis of the N-bonded monochlorosilanes afforded the N-bonded monosilanols ArN(SiMe₃)SiMe₂OH [Ar = C₆H₅ (2a), Ar = 2,6-Me₂C₆H ₃ (2b) and Ar = 2,6-iPr₂C₆H₃ (2c)]. The X-ray crystal structure of le reveals a positional disorder of the Cl and CH₃ substituents on silicon. The X-ray crystal structure of 2c shows that it is involved in an intermolecular O-H...O hydrogen bonding in the solid state to afford a dimeric structure containing the O₂H ₂ ring. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200401013

FULL PAPER
N-Bonded Monosilanols: Synthesis and Characterization of ArN(SiMe3)
SiMe2Cl and ArN(SiMe3)SiMe2OH (Ar = C6H5, 2,6-Me2C6H3,
2,6-iPr2C6H3)
Vadapalli Chandrasekhar,*[a] Ramamoorthy Boomishankar,[a] Ramachandran Azhakar,[a]
Kandasamy Gopal,[a] Alexander Steiner,[b] and Stefano Zacchini[b]
Keywords: Monosilanols / N-Bonded silanols / Hydrogen bonding / Aminosilanols
By the use of aniline and the sterically hindered aromatic
primary amines, 2,6-Me2C6H3NH2 and 2,6-iPr2C6H3NH2, N-
bonded monochlorosilanes, ArN(SiMe3)SiMe2Cl [Ar = C6H5
(1a), Ar = 2,6-Me2C6H3 (1b) and Ar = 2,6-iPr2C6H3 (1c)] have
been prepared by a sequential deprotonation at the nitrogen
followed by reaction with silyl chlorides. Hydrolysis of the N-
bonded monochlorosilanes afforded the N-bonded monosil-
anols ArN(SiMe3)SiMe2OH [Ar = C6H5 (2a), Ar = 2,6-
Me2C6H3 (2b) and Ar = 2,6-iPr2C6H3 (2c)]. The X-ray crystal
structure of 1c reveals a positional disorder of the Cl and CH3
substituents on silicon. The X-ray crystal structure of 2c
shows that it is involved in an intermolecular O–H···O hydro-
gen bonding in the solid state to afford a dimeric structure
containing the O2H2 ring.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
RRЈRЈЈSiOH are the simplest examples as these contain
only one Si–OH group per molecule.[8] Although several
types of monosilanols are known,[8] there are none which
contain Si–N bonds. One of the possible reasons for this
lacuna is probably the high sensitivity of the Si–N bond
towards hydrolysis.[9] On the other hand about 70 to 80%
of all silanols are actually synthesized by a hydrolysis reac-
tion of an appropriate Si–X bond (X = F, Cl, Br, I or
OR).[8] Recent pioneering efforts of Roesky and co-
workers,[10] and our interest in N-bonded silanols[11] has
prompted us to assemble N-bonded monosilanols. Accord-
ingly, herein, we report the synthesis and spectroscopic
characterization of ArN(SiMe3)SiMe2Cl [Ar = C6H5 (1a),
2,6-Me2C6H3 (1b), 2,6-iPr2C6H3 (1c)] and ArN(SiMe3)-
SiMe2OH [Ar = C6H5 (2a), 2,6-Me2C6H3 (2b), 2,6-
iPr2C6H3 (2c)]. We also report the X-ray structural charac-
terization of 1c and 2c.
Introduction
Silanols as compounds containing Si–OH units are at-
tracting considerable interest in recent years because of
various reasons. They are excellent precursors for the syn-
thesis of main group and transition metal siloxanes contain-
ing the Si–O–M bonds.[1,2] Thus, the reaction of appropriate
silanols with suitable metal substrates such as metal halide,
hydride, -alkyl, amide or alkoxide leads to the formation of
acyclic, cyclic or cage metallasiloxanes.[1,3,4] Often the na-
ture of the synthesized metallasiloxane depends on the type
of silanol chosen.[3] A second reason of interest in silanols
is their utility to serve as models for silica surfaces particu-
larly in the context of silica-supported transition metal cat-
alysts.[5] More recently, there has also been considerable
interest in silanols in organic synthesis.[6a] For example, sil-
anols have been found to be excellent substrates for palla-
dium-catalyzed (and fluoride-, cesium carbonate- or silver
oxide-activated) cross-coupling reactions.[6b–6d] The utility
of silanols in Mizoroki–Heck-type of coupling reactions
has also been demonstrated.[6e] Finally silanols are also
gaining importance as bioisosteres with specific interest as
transition-state analogues for metalloproteases, aspartic
proteases as well as HIV proteases.[7]
Results and Discussion
Synthesis and Spectra: Sterically unencumbered as well
as hindered aromatic amines (aniline, 2,6-dimethylaniline,
2,6-diisopropylaniline) were used as the starting materials.
Sequential deprotonation at nitrogen followed by reaction
with silyl halides afforded the N-bonded silyl chlorides 1a,
1b in excellent yields as distillable oils or as a solid (1c)
(Scheme 1). In contrast to the situation with corresponding
N-bonded silicon dichlorides and trichlorides 1b and 1c are
quite stable to ambient moisture. The compound 1a, how-
ever, is sensitive to ambient moisture and undergoes hydrol-
ysis to the silanol 2a.
Among the various types of silanols that have been re-
ported, monosilanols of the type R3SiOH, R2RЈSiOH and
[a] Department of Chemistry, Indian Institute of Technology, Kan-
pur,
Kanpur 208016, India
Fax: +91-512-2590007-2597436
E-mail: vc@iitk.ac.in
[b] Department of Chemistry, University of Liverpool,
Liverpool, L69 7ZD, U. K.
1880
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200401013
Eur. J. Inorg. Chem. 2005, 1880–1885

Synthesis and Characterization of ArN(SiMe3)SiMe2Cl and ArN(SiMe3)SiMe2OH
FULL PAPER
Scheme 2.
terized by chemical shifts for the –SiMe3 and –SiMe2Cl.
While the former resonate between δ = 11.9 and 12.6 ppm
the latter are seen at a slightly lower frequency between 7.8
and 8.6 ppm, respectively (Table 1). The –SiMe2Cl chemical
shifts occur at a higher frequency than the corresponding
Scheme 1.
Hydrolysis of 1a, 1b and 1c afford the corresponding –SiMeCl2 (–1.3 and –1.4 ppm)[11a] and –SiCl3 (–28.2 and
monosilanols 2a, 2b and 2c (Scheme 2). While hydrolysis of –27.9 ppm).[10a] A movement of the 29Si chemical shift to
1a is effected by the use of triethylamine as the hydrogen lower frequency occurs upon conversion of ArSiMe2Cl (1a–
chloride scavenger, hydrolysis of 1b and 1c require ammo- 1c) to ArSiMe2OH (2a–2c). Thus the latter resonate at –1.7
nium carbonate. It is important to note that the use of ani- (2a), –1.3 (2b) and –0.8 (2c) ppm, respectively. These chemi-
line, which is very effective as a mild base for the hydrolysis cal shifts are at a higher frequency in comparison to the
of N-bonded silicon dichlorides and trichlorides, does not corresponding silanediols (–29.4 and –29.6 ppm)[11a] and si-
result in clean hydrolysis of 1a, 1b or 1c. Although the silan- lanetriols (–66.2 and –65.3 ppm).[10a]
ols 2a and 2b are isolated as oils, 2c, which contains the
The IR spectra of the silanediols 2a and 2b in the solid
sterically hindered aromatic amine substituent, is a solid. sate in KBr pellets show broad bands at 3350 and
While 2a, 2b and 2c are rare examples of N-bonded monosi- 3416 cm–1, respectively. In 2c in addition to the peak at
lanols, 2a represents the first example of any silanol (mono- 3466 cm–1 a sharp peak at 3666 cm–1 is also observed. The
silanol, silanediol or silanetriol) where the sterically unen- observation of the latter shows that the formation of the
cumbered aniline is the substituent on silicon.
KBr pellet disrupts some of the intermolecular hydrogen
The new N-bonded silyl chlorides and silanols are ex- bonding in 2c to give rise to free Si–OH.
tremely lipophilic and are soluble in a wide range of organic
X-ray Crystal Structures of 1c and 2c: The X-ray crystal
solvents. The compounds 1a–c and 2a–c have been charac- structure of 1c shows a positional disorder; the Cl and CH3
terized by mass spectroscopy, elemental analysis, IR spec- groups attached to silicon are disordered over the same sites
troscopy and multi-nuclear NMR spectroscopy. The silyl (Figure 1). Such a positional disorder occurs because of the
chlorides and the monosilanols show prominent parent ion similar volumes of the Cl and CH3 groups. This results in
1
peaks in their FAB mass spectra. The H NMR spectra of the two Si–N distances being the same [1.729(1) Å]. The
these compounds are consistent with their structures. The sum of the bond angles around nitrogen N1 equal 360° re-
29Si {1H} NMR spectra of the silyl chlorides are charac- flecting the perfect planarity around nitrogen.
Table 1. 29Si NMR chemical shifts of N-bonded silicon chlorides and silanols and related dichlorides, trichlorides, diols and triols.
Compound
δ NSiMe3
δ SiCl
δ SiCl2
δ SiCl3
δ SiOH
δ Si(OH)2 δ Si(OH)3
Ref.
(C6H5)N(SiMe3)(Me2SiCl)
11.9
12.3
12.6
5.0
5.0
5.0
10.3
10.4
5.7
8.6
7.8
7.8
this work
this work
this work
this work
this work
(2,6-Me2C6H3)N(SiMe3)(Me2SiCl)
(2,6-iPr2C6H3)N(SiMe3)(Me2SiCl)
(C6H5)N(SiMe3)(Me2SiOH)
(2,6-Me2C6H3)N(SiMe3)(Me2SiOH)
(2,6-iPr2C6H3)N(SiMe3)(Me2SiOH)
(2,6-Me2C6H3)N(SiMe3)(MeSiCl2)
(2,6-iPr2C6H3)N(SiMe3)(MeSiCl2)
(2,6-Me2C6H3)N(SiMe3)(MeSi(OH)2)
(2,6-iPr2C6H3)N(SiMe3)(MeSi(OH)2)
(2,6-Me2C6H3)N(SiMe3)SiCl3
–1.7
–1.3
–0.8
this work
[11a]
–1.3
–1.4
[11a]
[11a]
[11a]
[10a]
[10a]
[10a]
[10a]
–29.4
–29.6
5.6
12.5
12.2
7.7
–28.2
–27.9
(2-Me-6-iPr2C6H3)N(SiMe3)SiCl3
(2,6-Me2C6H3)N(SiMe3)Si(OH)3
(2-Me-6-iPr2C6H3)N(SiMe3)Si(OH)3
–66.2
–65.3
7.5
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V. Chandrasekhar, R. Boomishankar, R. Azhakar, K. Gopal, A. Steiner, S. Zacchini
FULL PAPER
other silanols. This value is shorter than the sum of the
covalent radii of silicon and oxygen (1.74 Å). The geometry
around nitrogen (N1) is perfectly planar with all the angles
around it totaling to 360°.
Intermolecular hydrogen bonding in monosilanols can
give rise to different types of arrangements in the solid state,
such as a linear dimer,[14a] cyclic dimer,[14b] tetramer,[14c] zig-
zag polymer[14d] etc. The N-bonded monosilanol 2c shows
a cyclic dimer formation (Figure 3) which is quite rare and
has been shown before only by the monosilanols containing
direct Si–M bonds viz., [(η5-Cp*)Ru(CO)2]Si(o-Tolyl)2-
(OH)[14b] and [(η5-Cp)Fe(CO)2]2Si(H)(OH).[14e] In the solid
state two molecules of 2c interact with each other and form
a planar four-membered O2H2 ring. The intermolecular
H···O distance is 2.057(1) Å, while the O···O contact is
2.857(2) Å. The O–H···O angle is 158.94(9)°. It is of interest
to compare these parameters with those observed earlier.
Thus for {(η5-Cp*)Ru(CO)2}Si(o-Tolyl)2(OH) the hydrogen
bonding parameters are H···O, 2.172(27) Å. O···O,
2.809(32) Å and O–H···O 134.57(2)°. For {(η5-Cp)Fe-
Figure 1. ORTEP diagram of 1c shown at the 50% probability
level. All the hydrogen atoms are omitted for clarity.
(CO)2}2Si(H)(OH) these values are 2.197 and 2.991 Å and
157.95°.[14b] Thus, the observed hydrogen bonding parame-
The ORTEP diagram of 2c is shown in Figure 2. Unlike
in 1c two types of Si–N bond lengths are seen viz., Si1–N1,
1.731(1) and Si2–N1, 1.759(1) Å. The longer bond distance
is associated with the silicon bearing less electronegative
substituents while the shorter distance is associated with N-
SiMe2OH. The shorter Si1–N1 distance is however, longer
than the corresponding distance of 1.7140(18) Å observed
in 2,4,6-Me3C6H2–N(SiMe3)SiMe(OH)2. The Si1–O1 dis-
tance of 1.648(2) Å is consistent with the trends found in
Figure 3. (Top). Formation of a cyclic dimer due to intermolecular
hydrogen bonding between two silanol molecules. (Bottom). A per-
fectly planar arrangement of the four-membered O2H2 ring. The
metric parameters are: O1–H1, 0.840(1) Å; H1···O1*, 2.057(1) Å;
O···O*, 2.857(2) Å; O–H···O*, 158.94(9)°; symmetry, 1 – x, 1 – y,
2 – z.
Figure 2. ORTEP diagram of 2c shown at the 50% probability
level. All the hydrogen atoms have been omitted except those of
the hydroxy group.
1882
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Synthesis and Characterization of ArN(SiMe3)SiMe2Cl and ArN(SiMe3)SiMe2OH
FULL PAPER
Synthesis of N-Bonded Monosilanols. Synthesis of C6H5N(SiMe3)-
SiMe2OH (2a): solution of C6H5N(SiMe3)SiMe2Cl (1a)
ters in 2c are quite reasonable and indicate the presence of
a strong intermolecular hydrogen bonding.
A
(12.2 mmol) in Et2O (50 mL) was added to a well-stirred mixture
of Et2O (50 mL), water (12.2 mmol) and triethylamine (12.2 mmol)
at 0 °C over a period of 1 h. It was then allowed to come to room
temperature and stirred for 30 h. The precipitated triethylamine hy-
drochloride was filtered. Removal of solvent from the filtrate in
vacuo afforded 2a as a colorless oil.
Conclusions
In conclusion we have demonstrated the synthesis of the
new examples of N-bonded monosilanols. These syntheses
were accomplished starting from aromatic amines. A high-
light of the synthesis was that for the first time unsubsti-
tuted aniline could be utilized to afford an N-bonded sil-
anol. X-ray crystal structure of the monosilanol 2c showed
the presence of a hydrogen bonded dimer in the solid-state.
All the silanols are extremely lipophilic and air-stable. The
utility of these N-bonded monosilanols in the assembly of
metallasiloxanes is under investigation.
Synthesis of 2b and 2c: RN(SiMe3)SiMe2Cl (1b and 1c) (12.0 mmol)
in diethyl ether (20 mL) was added dropwise through a pressure-
equalizing funnel for about 30 min into a rapidly stirred two-phase
system consisting of 20 mL of water, 20 mL of diethyl ether and
1.0 g (10.0 mmol) of freshly titrated ammonium carbonate and so-
dium chloride (7.0 g). The solution was then stirred for another
2 h. The ether layer was separated and the aqueous layer was ex-
tracted twice with ether. The combined ether fractions were dried
to get crude 2b and 2c. The compound 2b was purified on a neutral
alumina column using n-hexane/ethyl acetate (90:10) as the eluent
to get a pale yellow oil. Compound 2c was purified by repeated
recrystallization from a solution of n-hexane.
Experimental Section
Characterization Data for Compounds 1a–c and 2a–c
General Remarks: All manipulations and reactions were carried out
under dry nitrogen by employing standard Schlenk techniques. Sol-
vents were dried with sodium benzophenone ketyl and were col-
lected from the still at the time of reaction. 2,6-Dimethylaniline
and 2,6-diisopropylaniline (Fluka) were distilled under reduced
pressure before use. Chlorotrimethylsilane, dichlorodimethylsilane
(Fluka) and n-butyllithium (2.5 m solution in hexane) (Aldrich)
were used as such without any further purification. Aniline (Spec-
trochem, India) was stored over CaH2 and distilled before use. In-
frared spectra were recorded in dichloromethane solution as well
as neat liquid or as KBr pellets with a FT-IR Bruker-Vector Model.
Elemental Analyses were performed with Thermoquest CE instru-
ments CHNS–O, EA/110 model. FAB mass spectra were recorded
with a JEOL-SX 102/DA-6000 mass spectrometer/data system
using argon/xenon (6 kV, 10 mA) as the FAB gas. The accelerating
voltage was 10 kV, and the spectra were recorded at room tempera-
ture. EI mass spectra were obtained with a JEOL-d-300 spectrome-
[C6H5N(SiMe3)SiMe2Cl] (1a): Yield 14.7 g (75.9%). B.p. 135 °C/
0.08 Torr. C11H20ClNSi2: calcd. C 51.23, H 7.82, N 5.43; found C
51.04, H 7.31, N 5.31. Mass spectrum (EI): m/z = 258 (41.5) [M]+,
(1 Cl isotope pattern). 1H NMR (400 MHz, CDCl3): δ = 6.85–7.08
(m, 5 H, aromatic), 0.22 [s, 6 H, Si(CH3)2Cl], 0.00 [s, 9 H, Si(CH3)]
ppm.
[2,6-Me2C6H3N(SiMe3)SiMe2Cl] (1b): Yield 15.2 g (75.9%). B.p.
143 °C/0.08 Torr. C13H24ClNSi2: calcd. C 54.60, H 8.46, N 4.90;
found C 54.22, H 8.17, N 4.55. Mass spectrum (FAB): m/z = 286
(29) [M+] (1 Cl isotope pattern). 1H NMR (400 MHz, CDCl3): δ =
6.76–6.84 (m, 3 H, aromatic), 2.13 (s, 6 H, C–CH3), 0.20 [s, 6 H,
Si(CH3)2Cl], 0.00 [s, 9 H, Si(CH3)] ppm.
[2,6-iPr2C6H3N(SiMe3)SiMe2Cl] (1c): Yield 16.9 g (66.0%). M.p.
108 °C. C17H32ClNSi2: calcd. C 59.69, H 9.43, N 4.09; found C
59.59, H 8.55, N 3.89. Mass spectrum (FAB): m/z = 342 (45) [M+]
(1 Cl isotope pattern). 1H NMR (400 MHz, CDCl3): δ = 6.89–6.96
(m, 3 H, aromatic); 3.30 [septet, 3J(H,H) = 6.8 Hz 2 H, HC-
(CH3)2], 1.03 [d, 3J(H,H) = 6.84 Hz, 6 H, CH–CH3], 1.04 [d,
3J(H,H) = 6.8 Hz, 6 H, CH–CH3], 0.21 [s, 6 H, Si(CH3)2Cl], 0.00
[s, 9 H, Si(CH3)] ppm.
1
ter. The 29Si {1H}, and H NMR spectra were recorded in CDCl3
solutions with a JEOL JNM LAMBDA 400 model spectrometer.
Chemical shifts are reported with respect to TMS.
Synthesis: The N-bonded monochlorosilanes 1a, 1b and 1c and the
corresponding silanols 2a, 2b, and 2c were synthesized by adopting
the following general synthetic procedure. The 29Si NMR spectro-
scopic data for these compounds along with some of the other
related compounds are listed in Table 1.
[C6H5N(SiMe3)SiMe2OH] (2a): Yield 2.7 g (82.1%). C11H21NOSi2:
calcd. C 55.17, H 8.84, N 5.85; found C 54.64, H 8.43, N 5.42. H
NMR (400 MHz, CDCl3): δ = 6.81–7.14 (m, 5 H, aromatic), 0.01
[s, 6 H, OSi(CH3)], 0.00 [s, 9 H, Si(CH3)] ppm.
1
Synthesis of the N-Bonded Monochlorosilanes, ArN(SiMe3)SiMe2Cl
(1a–1c) [Ar = C6H5 (1a), R = 2,6-Me2C6H3 (1b), 2,6-iPr2C6H3 (1c)]:
n-Butyllithium (75 mmol) was added at a constant rate to a solu-
tion of RNH2 (75 mmol) in diethyl ether (60 mL) at –78 °C. The
reaction mixture was stirred at this temperature for 4 h and then
brought to ambient temperature. It was then treated with a solution
of Me3SiCl (75 mmol) in diethyl ether (40 mL) at –78 °C and al-
lowed to come to room temperature. The precipitated LiCl was
filtered and the filtrate was treated with nBuLi (75 mmol) at room
temperature. After heating under reflux for 4 h the solution was
transferred to a pressure-equalizing funnel and added drop wise to
a solution of Me2SiCl2 (75 mmol) in diethyl ether (40 mL) and
stirred overnight. The precipitated LiCl was filtered and the vola-
tiles from the filtrate were removed in vacuo to give a yellow vis-
cous oily product. Subsequent vacuum distillation afforded the
pure silicon chlorides 1a and 1b as colorless oily liquids. Com-
pound 1c was isolated as a solid.
[2,6-Me2C6H3N(SiMe3)SiMe2OH] (2b): Yield 2.6 g (76.0%).
C13H25NOSi2: calcd. C 58.37, H 9.42, N 5.24; found C 58.21, H
9.08, N 5.11. Mass spectrum (FAB): m/z = 267 (47) [M]+. 1H NMR
(400 MHz, CDCl3): δ = 6.75–6.89 (m, 3 H, aromatic), 2.16 (s, 6 H,
C–CH3), 0.02 [s, 6 H, OSi(CH3)2], 0.00 [s, 9 H, Si(CH3)] ppm.
[2,6-iPr2C6H3N(SiMe3)SiMe2OH] (2c): Yield 3.5 g (87.0%). M.p.
108 °C. C17H33NOSi2: calcd. C 63.09, H 10.28, N 4.33; found C
63.19, H 9.52, N 4.18. Mass spectrum (FAB): m/z = 323 (70)
[M]+. 1H NMR (400 MHz, CDCl3): δ = 6.92–7.13 (m, 3 H, aro-
3
matic), 3.35 [m, 2 H, HC(CH3)2, J(H,H) = 6.84 Hz], 1.07 [d, 6 H,
3
3
CH–CH3, J(H,H) = 6.84 Hz], 1.08 [d, J(H,H) = 6.56 Hz, 16 H,
CH-(CH3)], 0.04 [s, 6 H, OSi(CH3)], 0.00 [s, 9 H, Si(CH3)] ppm.
X-ray Crystallography: Crystals of 1c and 2c were grown from a
solution of n-hexane at –20 °C. Colorless block-like crystals suit-
able for single-crystal X-ray diffraction were loaded with a Bruker
Eur. J. Inorg. Chem. 2005, 1880–1885
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V. Chandrasekhar, R. Boomishankar, R. Azhakar, K. Gopal, A. Steiner, S. Zacchini
Table 2. Summary of crystal and structure refinement data for compounds 1c and 2c.
FULL PAPER
Identification code
1c
2c
Empirical formula
Formula mass
Temperature
Wavelength
Crystal system
Space group
C17H32ClNSi2
342.07
213(2) K
0.71073 Å
orthorhombic
Cmcm
C17H33NOSi2
323.62
150(2) K
0.71073 Å
triclinic
¯
P1
Unit cell dimensions
a = 12.0741(18) Å, α = 90°
b = 12.2739(14) Å, β = 90°
c = 14.1562(16) Å, γ = 90°
2097.9(5) Å3
4
a = 8.4094(5) Å, α = 86.8540(10)°
b = 9.6229(6) Å, β = 81.5790(10)°
c = 13.0896(8) Å, γ = 71.3230(10)°
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
992.61(10) Å3
2
1.083 Mg/m3
1.083 Mg/m3
0.179 mm–1
356
0.292 mm–1
744
0.4×0.3×0.3 mm3
2.37 to 24.34°
0.5×0.5×0.4 mm3
1.57 to 28.28°
–14 Յ h Յ 13, –13 Յ k Յ 13, –16 Յ l Յ 16 –10 Յ h Յ 11, –7 Յ k Յ 12, –16 Յ l Յ 16
Reflections collected
Independent reflections
Completeness to θ
Absorption correction
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
Largest diff. peak and hole
6518
6325
915 [Rint = 0.0482]
96.9% (θ = 24.34°)
none
4384 [Rint = 0.0410]
89.1% (θ = 28.28°)
none
Full-matrix least-squares on F2
915/1/71
Full-matrix least-squares on F2
4384/0/200
1.100
0.986
R1 = 0.0399, wR2 = 0.1091
R1 = 0.0482, wR2 = 0.1130
0.214 and –0.216 e·Å–3
R1 = 0.0394, wR2 = 0.1032
R1 = 0.0480, wR2 = 0.1076
0.343 and –0.333 e·Å–3
AXS Smart Apex CCD diffractometer. The details pertaining to
the data collection and refinement for 1c and 2c are given in
Table 2. The structures were solved by direct methods using
SHELXS-97 and refined by full-matrix least-squares on F2 using
SHELXL-97.[12,13] The hydrogen atom attached to oxygen atom
was located from the difference map and its position was refined.
All other hydrogen atoms were included in idealized positions, and
a riding model was used. Non-hydrogen atoms were refined with
anisotropic displacement parameters. Selected bond lengths and
bond angles of 1c and 2c are given in Table 3 and Table 4.
CCDC-229758 and -229759 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Table 3. Selected bond lengths [Å] and angles [°] for 1c.
Bond lengths
N1–Si1
Si1–Cl1
Si1–C7
1.729(1)
2.110(5)
1.853(8)
Si1–C8
Si1–Cl1#3
N1–C1
1.857(4)
2.110(5)
1.478(4)
Acknowledgments
Bond angles
We are thankful to Department of Science and Technology, New
Delhi, India for financial support. AS thanks EPSRC (Engineering
and Physical Sciences Research Council), U. K. for financial sup-
port.
N1–Si1–C8
C8–Si1–Cl1
N1–Si1–C7
Cl1#1–Si1–
C7#1
108.51(12)
103.51(21)
113.42(33)
15.33(27)
N1–Si1–Cl1
Cl1–Si1–Cl#1
C8–Si1–C7
Cl1–Si1–C7
107.76(22)
124.83(16)
113.19(31)
109.86(25)
C7–Si1–C7#1
C1–N1–Si1*
94.74(34)
117.46(3)
C1–N1–Si1
Si1–N1–Si1*
117.46(3)
125.08(5)
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Si1–N1
Si2–N1
Si1–O1
1.731(1)
1.759(1)
1.648(2)
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119.17(9)
117.22(10)
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111.56(8)
103.86(7)
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Synthesis and Characterization of ArN(SiMe3)SiMe2Cl and ArN(SiMe3)SiMe2OH
FULL PAPER
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Received: December 10, 2004
Eur. J. Inorg. Chem. 2005, 1880–1885
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