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.

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).

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 )

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

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.

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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6 Nakamoto K, Infrared and Raman spectra of inorganic and coordination compounds, 4th Edn (John Wiley, New York) 1986.

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