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Indian Journal of Chemistry Vol. 41A, October 2002, pp.
2054-2059
Silyl-nitrogen compounds: Part XIII-Reactions of metal halides
with silylated tosylhydrazines
S K Vasisht*, P Venugopalan, lyoti Kataria & Anuradha
Sharma
Dept!. of Chemistry, Panjab University , Chandigarh- I 60014,
India
Received 24 December 2001; revised 10 lillie 2002
Bis(trimethylsilyl)tosylhydrazine (Me,SihTsN2H reacts with ECl n
(E=AI ,Sn ,Sb or Ti) to liberate MelSiCl and in the process form
tosylhydrazides, ECl n_I(Me, Si)TsN2H. These compounds decompose on
heating ill vacl/o to form a variety of azane derivatives with the
loss of volatile products like Me, SiCI, HCI or SbCI, .
Ditosyltetrazene intermediate decomposes into ditosylhydrazine
whose structure is determined by X-ray diffraction.
Tosylhydrazine is known to undergo silylation, germylation and
stannylation to form a variety of silylated, germylated and
stannylated tosylhydra-zines ' . Tosyl group has good leaving
properties and finds applications in numerous elimination and
substitution reactions. Some of these molecules are reported to
undergo lithiation to form lithium salts which decompose on heating
to give TsLi and cOITesponding diazene.
In the present investigations, reactions of some metal halides
with silylated tosylhydrazine have been done with a view to
understand the possible redox, substitution or elimination
reactions besides complexation.
Materials and Methods All the investigations were carried in the
absence of
air and moisture on a vacuum line connected to a dry nitrogen
supply system. Bis(trimethylsilyl)toluenesul-phonylhydrazine (I)
was prepared as reported in literature l . The IH NMR mesurements
were recorded on Varian EM390, IR spectra on Perkin-Elmer 621, mass
spectrum on VG analytical 11-2505-708 mass spectrometer and
elemental analysis on CarloErba strumentazione (Italy) elemental
analyser model 1106. Thermogravimetric analysis were done on
Perkin-Elmer 7 series thermal analysis system. The intensity data
for X-ray crystallographic studies were collected on Siemens P4
single crystal diffractometer equipped with molybdenum source (/..=
0.7 1073A) and highly oriented graphite monochromator.
General procedure Bis(trimethylsilyl)toluenesulphonylhydrazine
(I)
( 10 mmol, 3.3 gms) dissolved in 20 ml n-hexane at
room temperature or slightly lower temperature was reacted with
required amount (2011 0 mmol) of metal halides (ECI,,,
E=AI,Sn,Sb,Ti) dissolved III 11-hexane/benzene/THF. The reaction
mixture was stirred overnight. I H NMR spectrum of the reaction
mixture was recorded to monitor the progress of the reaction. It
was then fi Itered and the residue dried ill vacuo. The product
formed was thermolysed in vacuum. The volatile material was trapped
in liquid nitrogen trap/distilled in a glass baot/sublimed. The
compounds formed before thermolysis and after thermolysis were
characterised by 'H NMR, IR, mass spectra, elemental analysis and
thermogravimetric analysis.The compounds along with their
analytical data are listed in Tables 2 and 3.
X-ray crystallographic studies of compound (VII) were done as
follows: A single crystal with dimension 0.36xO.26xO.19mm was
mounted along the largest dimension and used for data collection.
The lattice parameters and standard deviations were obtained by
least squares fit to 40 reflections . The data were collected by
28-8 scan mode with a variable scan speed ranging from 2.0° to a
maximum of 45.0°ltnin. Three reflections were used to monitor the
stability and orientation of the crystal and were remeasured after
every 97 reflections . Their intensities did not change
significantly during 35.06 hrs. X-ray exposure time. The data were
conected by Lorentz and polarization factors.
The structure was solved by direct methods using SHELX-972
package and was also refined using the same. All the non-hydrogen
atoms were refined anisotropically. The hydrogen atoms were
included in the ideal positions with fixed isotropic U values and
were riding with their respective non-hydrogen atoms.
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V ASISHT et at.: STUDIES OF SIL YL-NITROGEN COMPOUNDS 2055
Table 1- Crystal data and structure refinement parameters of
compound (VU)
Empirical formula
Formula weight
Crystal system, Space group
Unit cell dimensions
Volume
Z, Calculated density
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Weighting scheme
P=(max[Fo 2,0)+2*Fc2]/3
Final R indices, 2168 reflections [1>20(1)]
R indices (a ll data)
Largest diff. peak and hole
The refinement converged to a final R value of 0.0371
(wR2=0.0969) for 2168 reflection [1>2cr(l)]. The final
difference map was featureless. All relevent informations are
recorded in Table I.
Results and Discussion
Bis(trimethylsilyl)toluenesulphonylhydrazine (I)
reacts with butyllithium to form its lithium salt which
decomposes on heating 117 vacuo to provide bi
s(trimethylsilyl)diazene, MeJSiN=NSiMeJ} . Similarly ,
lithiumtosylhydrazine decomposes in vacuum at higher temperature to
form diazene H2N24 .
In the present investigations, aluminium(iII) chloride has been
found to react with bis(trimethyl-sily l)toluenesulphonylhydrazine
(I) at room temperature to form
dichloro(trimethylsilyltosyl-hydrazine) aluminium(IlI), (II).
Ts, , H Ts, )"1 N - N + AICI.1 _ N - N + Mc,SiC'l
Me.,S( 'SiMe, AiCI{ 'SiMe.1
(I ; (II )
Compound (II) is a white crystalline solid soluble in polar
organic solvents. Important IH NMR values and IR bands (cm- I)5.6
characteristic of (II) are listed in Table 2. Mass spectrum (70eV)
shows molecular
C I4 HI 6 N2 0 4 S2
340.41
Monoclinic, P2 1/c
a= 15.788(l)A
b = 10.731(1) A
c = 9.501(1) A
1609.7(2) A3
4, lA05 Mg/m3
0.36 x 0.26x 0.19 mm
2.29 to 24.00°.
0~h~18,-12~k~0,-10~1~10
2626
2529 [R(int) = 0.0177]
Full-matrix least-squares on F2
2529/0/207
1.053
1/[ 0 2(F02)+(0.050 I p)2 +0.59P],
Rl = 0.0371, wR2 = 0.0969
Rl = 0.0448, wR2 = 0.1030 , 3
0.237 and -0.259 e.A-·
ion peak at rnJz 354. It decomposes on heating 111 vacuum to
form (III) by the following route:
11 o I
-0-'1: II ,N-SiMC3 H,C S-N . - II ''AI-Ci o I (II) CI
o H1C-o-'I: ~-N
. - I I o N
( III ) ',{(
-. MC3SiCI 11 o '
H1C-o-'I: ~- N'I - II 'AI
o 'CI
J ·HCI
J 0 '
H1C-o-'I: M-N-N l l · - II \11 I o AI )
IH NMR of (III) in d6-DMSO shows the absence of silyl protons.
IR spectrum of sulphone group O=S=O is reportedS to show two strong
bands around 1300 and 1150 em-I. As expected this has not been
observed in (III) which shows only one band at 1090 em-I due to
v(S=O).
Thermogravimetric analysis of (III) in pure air and nitrogen
shows that it behaves like a salt (Fig. I)
decomposing to AbO] at 550DC in air. In nitrogen
decomposition at 1000De contains mainly A120~ contaminated with
small amount of carbon.
Reaction between SbCls and (I) at low temperature (_40DC)
provides a substitution product tetrachloro-(tri methy lsi Iy I
tosy Ihydrazino )antimony(V),(IV).
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2056 INDIAN J CHEM, SEC A, OCTOBER 2002
Table 2- Analytical data of silylated tosylmetalhydrazines
Reactants Compound (molar ratio)
(I ) : EX n
1:1 Ts(AICI2)N-NH(SiMej) (AICI 3) (II)
TsAIN2 (III)
1:1 Ts(SbCI4)N-NH(SiMej) (S bCIs) . (IV)
Ts2N4H2 (VI)
TsN2H2 (VII )
1:1 Ts(TiClj)N-NH(SiMej) (TiCI4 ) (VIII )
TsN2HTiCl 2 (IX)
2:1 [Ts(SiMe,)N2HhSnCI2 (S nCI4 ) (Xl)
Sample Weight: 24.199 mg
24.00 2.00 .,
.,...--- ------- ~ .----_._\( -2.00 " 20.00 . !:
\ '\ .I 'i E \"'.J ' / I. -6.00 "-16.00 '\... ' I '" -;. I.
E
5 '1 -10.00 12. 0 0 !. '" :c .:: '" -14.00 0 '"
B.O O > ~ -18 .00 ..
4.00 0
-22.00 :0 0. 00
100.0 300.0 500.0 700.00 TEMPERATURE (oC )
Fig. 1- Therillogra vimciri c analys is of (III )
Ts, / H Ts, / H N- N + ShCls
Me,S( 'S iMe, ---... N-N -Me,SiCI Cl.;stf 'SiMej
(I) (IV)
Compound (IV) is a very hygroscopic white solid so luble in
polar organic solvents. Its IH NMR in
d6-DMSO shows a signal at 8 0.23 ppm due to Me3Si group.
Molecular ion peak is observed at m/Z 520.
Compound (IV) is not stable and decomposes at SSUC in vacuo. The
decomposition occurs with sublimation of SbCb and simultaneously
chlorotri-methylsilane is released into a cold trap. The
residue
Found (Calc), % C H N X M
33.20 4.20 7.60 19.80 7.20 33.80 4.79 7.88 20.00 7.60
38.64 3.29 13.12 0.00 12.46 40.00 3.33 13.33 0.00 12 .86
22.70 3.00 4.90 26.70 23.10 23 .03 3.26 5.37 27 .25 23.40
45 .21 4.1 6 15.33 0.00 U.OO 45.65 4.35 15.22 0.00 0.00
47.94 4.64 8.43 0.00 Cl.OO 49.41 4.70 8.23 0.00 0.00
28 .84 4.00 6.36 25. 80 11.2S 29.16 4.1 3 6.80 25.88 11.66
26.94 2.54 9.02 23.00 15 . 11 27.72 2.64 9.24 23.43 15.84
33.96 4.69 8.01 10.10 16.37 34.10 4.83 7.96 10.09 16.87
left behind is a white solid (VI) stable upto lOO°e. Elimination
of SbCI 3 and Me,SiCI indicate the possible formation of
tosyldiazene Ts-N=N-H (V) as an unstable intermediate .
ssOC IvacuuITI. -ShCI,
(I V)
! Ts-N= N -H\ l . )
(V )
Inorganic diazenes are usually unstable and decompose easily
under disproportionati on, dimerisation or cleavage7 . Although di
sproportiona-tion is the most prominent mode of decomposition but
tosyldiazene (V) does not seem to undergo disproportionation as
there is no liberation of nitrogen. The compound (VI) may either be
a tetrazene formed by di merisati on or a tetracyc lo-butane
derivative formed by cyclisation of (V). However, tetrazene is
favoured and supported by the
thermolysi s of (VI) when it decomposes at lOO°C to lose
nitrogen and form the hydrazine Ts(H)N-N (H)Ts (VII).
Ts, / Ts N- N=N - N
/ , H H
IOOOC ~
(VI ) (VB )
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V ASISHT et at.: STUDIES OF SIL YL-NITROGEN COMPOUNDS 2057
Table 3-NMR, IR and mass spectral data of compounds (II) to
(XI)
Compound 'HNMR I R values Mass spectrum (70 eV) Solvent Position
Area & mlz major fragment
Assignment
(II) CDCI, 0.42 9H, Me)Si 3320,3150v(NH),1310,1 150v 354(m +)
,290(m-S02t , 2.40 3H,CH)(Ts) (S02) 440v(AIN),380v(AICI)
199(m-Tst,97(AICI2t
(III) d6-DMSO 2.40 3H, CHJ(Ts) 1595v(C=C), 1090v(S=0)
209(m+),194(m-CH.1t
950v(S=N),885v(S-0) 155(C7H7S02),145(m-S02t
(IV) d6-DMSO 0.23 9H ,Me3Si 3315,3270v(NH),1074v(N-H) 520(m
+),456(m-SOl t 2.42 3H,CHJ(Ts) 758v(Si-N),554v(Sb-N),397v(SbCI)
447(m-Me, Sit,365(m-Tst
THF 0.17 9H, Me3Si 291(SbCI2t ,9 I (C7H7t 2.40 3H, CH3(Ts)
(VI) d6-DMSO 2.38 3H, CH3(Ts) 3330v(NH),1595v(C=C),
368(m+),340(m-N2t 7.34 4H, Ar(A2B2) 131O, 1140v(S02),l045v(N-N)
304( m-S02t ,213(m-Ts t
184(Ts-N=N-Ht.155(Tst
(VIII) d6-DMSO 0.08 9H, Me1Si 3320v(NH),1595v(C=C)
412(m+),377(m-CH, t 2.38 3H, CH3(Ts) 1300, 1130v(SOl), 1013v(N-N)
339(m-SiMe, t ,257(m-TiCl,t 3.30 IH,NH 515v(Ti-N),390v(TiCl)
190(TiClt,184(TsN=NHt
155(Tst,91 (C7H7),73(S iMe,t
(IX) d6-DMSO 2.39 3H, CHJ(Ts) 3335v(NH),1595v(C=C) 302(m
+),287(Ill-Met 7.35 4H, Ar(A1B2) 1130v(S=0),935v(S=N),
267(Ill-Clt,250(Ill-Me3SiN=NHt
575v(Ti-N),390v(TiCI) 184(m-TiCI2), 155(Tst, 91(C7H7t
(XI) d6-DMSO 0.33 9H, Me, Si 331 0,3160v(NH), 1595v(C=C), 2.40
3H, CH, (Ts) 1305, 1140v(S02),81 Ov(Si-N),
550v(Sn-N)
Compound (VII) is a white solid soluble in CH2Ch. It was
crystallised from 1: 1 mixture of CH2CI2 and 1/.-hexane.
Titanium(lV)chloride reacts with (I) at low temperature in I: I
ratio to form a substitution product trichloro(tri methy Itosy
Ihydrazi ne )ti tanium(IV), (VIII).
1's, / H N- N + TiC~ ---
MqS( ' SiMc, - Me,SiCl
Ts, )1 N-N
C!.1T( ' SiMe, ( I) (VIII )
Compound (VIII) is a hygroscopic white solid soluble in polar
organic solvents. Its 'H NMR in
d6-DMSO shows a silyl signal at 8 0.08 ppm.Molecular ion peak in
the mass speclrum is observed at mlz 412 (m+) . It changes into a
white diamagnetic solid (IX) on thermolysis in vacuum at 120"CII
O-' torr when a molecule of chlorotrimethylsilane is lost.
o r·I, Hl -o-~ II .. l s, CH, S= N I s, ... H I :!OOOlO~J lorr
N-N/ _ I I
N- N • \ I - 0 N-H C,' I T./ 'S'M " Me,S iC! Ti j \ ( J I I c) /
\ rl
CI CI c ( 'C1 (VIII ) (IXA) (IX B)
Compound (IX) is soluble in DMSO and MeOH. Its IH NMR in d6-DMSO
shows absence of silyl protons.IR spectrum of sui phone O=S=O
species shows two bands at 1300 and 1150 cm -I whereas a sulphoxide
shows only one band around 1050-1100 cm- I and S=O linkage in
sulphites in the region 1100-1200 cm- I 5.6. The IR spectrum of
(IX) does not show
a band at 1300 cm- I thereby ruling out a sulphone
group. Instead a strong band at 1130 cm- I due to
v(S=O) and a band due to v(S=N) at 935 cm- I shows formation of
structure (IX B) . Formation of (IX B) can be envisaged through an
unstable intermediate (IX A), which on rearrangement produces more
stable (IX B).
Reaction of tin(lV)chloride with (I) at room temperature show
simple substitution to form stannylated tosylhydrazine derivatives
(X) and (XI).
'H NMR of the reaction mixture in THF shows
three major signals at 8 0.44(due to Me3SiCI), 0 .33 and 0.25.
The signal at 8 0.25 diminishes slowly with an increase in the
intensity of signal at 8 0 .32. The signal at 8 0 .25 is due to
Me,Si group protons of the compound (X). Compound (X) could not be
isolated in pure form and tends to undergo subsequent
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205 8 INDIAN J CHEM, SEC A, OCTOBER 2002
Ts, , H N-N + SnCL!
Me1S( 'SiMC:1
(I)
Ts, / SiMe:1 N-N
ChS,! 'HH - \ ,
N-N T( ' SiMC:1
(XI)
Fig. 2- A perspect ive view of the mo lecul e with ato m numberi
ng scheme. Thermal e llipsoids are at 50% probability .
substitution to form a white crys talline solid which was
characteri sed as di chlorobi s(trimethy lsilyltosyl-hydraz
ino)tin(lV ) (XI). Its 'H NMR in clc,-DMSO shows a signal at 8 0
.32 due to Me3Si group. Thermogravimetric analys is of (XI) in air
shows a multi step decomposotion upto 700°C to form Sn02 as a white
residue. Wei ght loss in nitrogen continues upto 900°C leav ing
behind g rey ish black tin and not Sn0 2. Almost all the steps of
thermal deco mposition in nit rogen were simil ar to those in air
except the te mperature ranges.
Crvs /o! structll r e Of colllfJo li lld (VIII) A perspective
view of the mo lecul e with atom
num bering scheme is g iven in Fig. 2 . The molecular confo
rmation of (VII) in solid state appears like a he li x (Fig. 2),
the torsional an gle of S(2)-N (2)-N(l )-S( I) bei ng - 12 1.6° and
the twist of the best least squares pl ane through the two phenyl
rings being 103.3°. In the crystal lattice, this symmetrically
subst ituted hydrazine derivati ve can in principle have
Fig.3- The N-H ... O hydrogen bonding network observed in the
crystal structure of (VII). The o ri entation of the hydrazi ne
hydrogens and the fo rmation of interlin ked 10 membered rings are
noteworthy
2-fold axis or mirror plane (or a combination thereof
leading to 1 ), but due to this helicity , the symmetry elements
are lost upon packing. It is also interesting to note that the
vicinal hydrogens of the hydrazine moiety are almost towards same
side (resembling ci s hydrogens, see Fig-A) , the torsional angle
H(l A )-N(1)-N(2)-H(2A) is -16.9° and the maximum deviation of N(2)
from the best pl ane comprising of NO ), H(1A), N(2), H(2A) is only
O.OS A. Such a molecular orientation is due to the presence of a
net work of hydrogen bonding that stabilizes the crystal lattice.
Both the hydrogens of the hydraz ine moiety take part in the N-H
... O hydrogen bonding. The sulphonate oxygens 0 (2) [N(2) . . . 0
(2) = 2.936A, H(2A) .. . 0 (2) = 2.204A, N(2)-H(2A)-0(2) = 163
.02°] and 0 (4) [N(I ) ... 0 (4) = 2.861,.\ , H(lA) ... 0 (4) =
2.211 A, N(1 )-H( IA)-0(4) = 154.1 9° ] take part in the format ion
of in finite interlinked ten membered rings that commonl y share
the hydrazine nitrogens (Fig. 3). The adjacent phenyl groups of thi
s ring adopt the commonly observed T shape packing of the benzene
rings . Thus, hydrophilic hydrogen bonded layers and the
hydrophobic hydrocarbon layers stack alternatively to produce the
three d imensi onal latti ce . It is interesting to note that the
other two sulphonate oxygens [i.e., 0(1 ) and 0 (3)] do not take
part in the N-H ... O hydrogen boding but po ints towards the
hydrogens of the hydrophobic region [0(1 ) .. . HCl4A)=2 .614 A, 0
(3) ... H(l 3A)=2 .60 AJ indicating the cooperati ve nature of C-H
... 0 interactions that contribute towards the overall stability of
the structure.
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V ASISHT et al. : STUDIES OF SIL YL-NITROGEN COMPOUNDS 2059
Acknowledgement The authors are thankful to the CSIR, New
Delhi,
for financial support.
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