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LEWIS.ACID CHEMISTRY OF SOME SULPHUR-NITROGEN' COMPOUNDS

By

JOHN DAYIa TYRER, B.Se.

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SUbmi tted to the Sqhoo'l of Graduate Studi es

in Partial Ful fi lment of t'h~ Requireme'nts.for" the Degre\,..\_•...:. ,', ' .

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Doctor of Ph'Hosophy,"

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McMaster Uhiversity

. ~ePte'!lber, 1978

'©. J.D, Tyrer, '1~78,

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LEWIS ACID CHEMISTRY OF SOME SULPHUR-NITROGEN COMPOUNDS.

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TO MY PAREIHS

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DOCTOR OF PHILOSOPHY(Chemistry) .

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McMaster Un~versityHamil ton, On~ario

v' TITLE: Lewis ACi, Chemistry of Some Sulphur-Nitrogen Compounds~ .

AUTHOR: Tyrer, ~.Sc. (McMa~ter u.niversityf

.sUPERV ISOR: or R.J . Gill espi e

:..~UMBER OF PAGES: . xvi, 203 .jI~ -

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ABSTRACT

The compound S4N4 has been shown to react with the Lewis acids

SbC1S' SbFS and AsFSto produce the previously unreported cyclotetra,-. 2' I

thiazyl dication, S4N4f, in the form of the salts S4N4(SbC16)2~ S4N4(SbF6)2'

, S4N4(AsF6)2'~S02' and S4 N4(Sbl14

)(SbF6)· A re.action sequenci~for the pre­

p'aration of S4N4(SbC16)2 has been sugges.ted and the infrared and'Raman_\..

spectra for, each of the salts is reported as w'ell as the crystal struc,.

,tures of the' S4N4,(SbC16)2 and S4N4.(:bl14)(Sb~6) salts',

A brief investigation ~f th~ r~action of S4N4 with. the Lewis

acids PFS. afld PC1 S p~oduced; i.n the Si-l4/PFS ,system, the ne\'I ~olecu-lar

adduct, S~N4 ,PFS': ~/hereas the reaction of S.4N4 wH~ PC1 S yLe1'dec(a"

complex mixture of products, composed of phosphonittilic chlorides",

The chemistry of trichlorocycl~trithia~ene~ith SbC1 S h?~ beenI

studied, ,It has been d~termined for the first time ,that S31'l3C13 when

oxidized'lby SbC1 S p'roduces the S4N4(SbC16)2 salt ~lith the co"!pounds

S4N4'SbC1S and SS~5(SbC16) isolated ai inter~ediates forme~ during'

the pr~duction of the S4'N~+, dicatio~, The crystal struct~res of 'both

S4tl4,SbCls and SSN S(SbC1 6) are reported i':l this th.esis'~, , • It

'In contrast, t~e fluoride, trifluorocyclotr~thiaz~ne,S3N3F3', . .

whe~ combin~d with the Lewis acids ,SbFS' AsfS .and S03 was no~ oxidlzed

but rather simple fluoride ion abstraction occurred t~yield the thialyl

salts SN (SbzF11), SN (As F6})and SN ('sal) ,For the f.irst time, the chemistry of the sulphur imides witb. "

Le~'1i s aci ds of oxi dati ve capab'i 1i ty has been s tudi ed,

Cyclotetrasulphurtetraimide, S4N4H4i ~e~cted readily with

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S4,N 4(S?CJ6)2, Trye 'compo~nd,s4nd'SbC1S

a~.'intertnediate armed du'rirtg the oxfdation ofSbCl q. to yi ehi. the

S4N4H4 with SbC1 S'. . "..' '.. .. .,

. Cyc 1, ohe'p t-asu 1phuri mi de, . S7'N:H, and 1',4.-.cyc 1ohexasu 1[)h ur.di i mi de',

1,4-S6NZH2 , produced the pre'ViOus1Y:"u.nkn~\'/~ '~,ithion~'troni-tJnJ 'ion, 'S2N+,:,

when treate~'w;tn' SbC1S

' . Infrared ~nd Raman-spectra i 9r the S2N(SbC15}.' , "T '"

are reported as well as'the crystal st,ructu:re.T. ;, 4 •

In a limited,investigation, th~ co.mpo~nq CllNPC13{PC16h has .,'• < • ,

been isolat'~d from the':eaction, of S7N~ W.i,th ,PelS.' !he cr~s,tal-st,~~c-:, ,

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ttl re 0 f the': tri.ch 1orp[ ( tri eh lora phos phora ny1idene )amim ] phosphorus (V)

hexach 1orophos pha teo is reported in tfl i s wbrk. ., .

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ACKNOlolLEDGEMEilTS

The author vlishes to express his sincere appreci at i on to

·all those ~ho contributed towards this thesis, in oarticular:

'To the 1ate Dr. F:P. 01 sen for his encouragement and gui dance

during the initial stages of this project;

,To Professor R.J, Gill~spie for his aid'and supervision

during the course of this work, and for the helpful discussions in

the prepara~~on of this thesis;

To pro D.R. Slim for the X-ray structural analyses of the.'

compounds S4N4(SbC16)2' S4N4(Sb3F14)(SbF6)' S4N4'SbC1 S and SSNS(SbC~6);

To Dr. C.J.L. Lock and Mr. R. Faggiani for the X-ray struc-

, tural determin~ti"On of S2N(SbC1 6);

To Dr. J. Sa\'tyer for the X-ray structural determination of

(C1 3PNPC1 3)(PC1 6);

To Mrs. Jan Gallo for her patience and care in typing this

thesis;

To Miss N.J. Railton for her care in doing many of the illus-

trations in this thesis;"'

'To Mr.' F. Ramelan for preparing .the spti!ctra for use in this

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TABLE OF CONTENTS

Pdge

ABSTRACT 'J i 1 i>,

ACKNOWLEDGEMENTS vI

TABLE OF CONTENTS vi

LIST .OF FIGURES"

LIST OF TABLES

.CHAPTER I - INTRODUCnON

1-1 . TheChem;stry of' S4N4

1-2 ·Reactions of S4N4

, (i) I{ith Lewis 'Bases

(ii) ~ith Lewis Acids

1-3 Trich1orocyc1otrithiazene.1-4 Trifluorbcyc1otrithiazene

1-5 The Chemistry of the Sulphur Imides

Cyc10heptasulphurimide

(i) Ring Cleavage

(ii) Addition Reactions

I' Cyc1ote'trasu1 phurtett'aimide

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11

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27.1-6 Bonding in Cyclic Su1'phur Nitrides (N'eutral., Anionic,

and Cationic Species)

1-7 Aims of the Present Work

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~HAPTER II - PREPARATION AND PURIFICATION OF STARTING MATERIALS 32

11-1 Preparation of S4N4

11-2 Preparation of S4N4H4

I 1-3 Prepara tion 0 f S7NH

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11-4 Preparation of S7NCH3

11-5 Preparatio.n of S3N3C13It

11-6 Preparation of S3N/3

11-7 Preparation and PurIfication of MaterialsI

11-8 General Experimental T~chniques

11-9 Instrumentation

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Infrared Sp~c troscopy

Raman Spectroscopy

Electron Spin Resonance Spectroscopy

Nuclear Magnetic Resohance Spectroscopy(a) 19F NMR Spectra

(b) 31 p NMR Spectra

Mass Spectroscopy

Dry Box

Ana 1ys es.

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CHAPTER III - LEWIS ACID CHEMISTRY OF S4N4

111-1 Reaction of S4N4 with Lewis ACIds

111-2 The PC1 S/S4N4 and PF S/S4N4 Systems

111-3 Raman and Infrared Spectra of the Molecular Adducts

of S4N4

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111-4 The ReactIon of S4N4 with Anhydrous HF 58

. 111-5 The Reaction of S4~4 with WF 6 in a 1:3 Mole RatIO 60

111-9 . Structure of the Cyclotetrathldzyl Oicatlon

111-10 The Sb3F~4 Anion

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I I 1-6

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The S4N4/SbC16 System

The S4N4/AsFS and S4N4/SbFS Systems2+Infrared and Raman Spectra of S4N4 Sa 1ty' t>

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Exper1menta 1 SE>C t Ion

The ReactIon of <; 1N, '0'/ i th a Ld r'le £xcec;" of SbCJ~• "t

The Reac t ion of S4N4 \'Ji th SbC 1 r. 1n d 1:3 Mole)

Rd t 10

The Reaction of S4 N4'SbC1 S with SbCl S 1n J 1: Z

Mo Ie Ru t 10

The ReactIon 9~4N4 wIth SbCl~ In a 1:2 MoleRa t 10

The ReactIOn of S4N4 with PF S In d 1:3 Mole

Ratio

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The Reaction of S4N4 wI th 'Anhydro'Js Hi=" In LiqUId S02

The Reaction of S4N4 .wi th WF ti 1n J 1,.:3 ~'ole RJt10..., . \

The-ReactIon of S4N4 wIth AsFS

In 1:3 and 1:6

~lo1e Ratios

) CHAPTER IV

IV-I

IV -2

IV - 3

IV -4\.

IV - S

IV -6

'"The Reaction of S4~4 with One Mole of PC1S in

CH2C1

2

The Reaction of S4N4 wi-th SbFS

In a J-:4 Ho Je RatIO

The ReactIon of S4N-l wi th 5bFS

ih (l 1 : 3 Mo 1e Rat 10

The Reaction of 54 N4 wi th Anhydrous HF

- THE LEI.JIS ACID CHEMISTRY OF S3N/13 and SIN/ 3

Reactions of S3Nl13 and S3N/3vWlth LeWIS t'\cld.,

The S3N3C13/SbC15 System

The S3N3F3/Lewi" ACId System

Mass Speclra of S3N/3 and S3~13C13

The Crystal Structure of SSN S(SbC16

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The Crystal Structure of S4N4'SbCIS

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CHAPTER Vf - 'SUMMARY~ CONCltJS fONS.I •

V1-1 lo~cJ~? lons/;'- '/ t,

VI-2 SuggeStions for Future Work

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BIBL IOGRAPHY.... '

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V-4 The Infrared and Raman Sp~ctra of (S2N)(SbC16)

v-s The Crystal 'Structure of S2N(SbC16)I

V-6 The S7NH/PC1S System

V-7 The Crystal Structure of (Cl 1P-N-PC1;)(PC1;)

V-8 Experimental Section

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V-3 +The Dithionitronium Ion, S2N

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The Reaction of Heptasulfurimide with SbC1 S in a1:2 Mole Ratio 176

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The Reaction of Heptasulphurimide with BC13

andSbC1 S

The Reaction .of 1,4-S6N2H2 with SbC1 S in a 1:4Mole Ratio

The Reaction of S4N4H4 with SbC1 S in a 1:3 MoleRatio

..IiThe R~action of S4N4H4 with SbC1 S in a 1:5 MoleRatio

The Reaction of S7NCH3 with SbC1 S in a 1:3 MoleRatio

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180

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The Reaction of S7NH with AsFS in a 1:3 Mole Ratio 181

The Reaction of S7NH with SbFS in a 1:3 Mole Ratio 181

The Reaction.of S7NCH3 with AsFS in a 1:10 MoleRatio '"18'2

The ~eaction of S7NH with PC1 S in a 1:2 Mole Ratio 182

The Reaction,of'S7NH with PFS in a 1:2 Mole Ratio 183

The Reacti~n of S7NCH3,with PFS in a 1:2 Mole Ratio 184

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IV-7 Bonding in. Su1phur- Nitrogen Ring Systems

IV-8 Experimental Section

The Reaction of S3N3C13 wit~ SbC15

in Liquid SO'2in a 1:2 Mole Ratio

The Reaction of S3N3C13 with SbC1 S in SOC1 2in a 1:2 Mole Ratio

The Reaction of S3N3C13 wi th SbC1 S in a 1: 2Mo 1e Ratio

1. The Reaction of S3N3Cl3 with SbC1 S in CH ZC1 Z ina1: 1 Mole Ra ti 0. \

\i~: The Reaction of S3N3C13 wi th SbC1 S in S02 in a 1:1It

Mole Ratio~

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'Preparation of S3N3C1'2(SbC'6) from the Reaction of

S3N3C13 with SbC1 S in CC1 4 in a 1:1 Mole Ratio

Solutions of S3N3C12(SbC16) in CH 2C'2 and S?2

Preparati on of. (SsNS)(SbC1 6 ) by the Method of

Banister

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The Reaction of S3Nl3 with S03 in a 1:3 Mole Ratio' 145

The ,~eaction of S3Nl3 with SbFS in a 1:6 Mole Ratio 146

The Reaction of S3N3F3 with SbFS in a ':2 Mole Ratio 146

The Reaction of S3N3F3 with AsF5 in a 1:6 Mole Ratio 146

The R~action of S3N3F3 with A~FS and SbFS in a 1:2Mole Ratio 147

CHAPTER V - 'THE ..,lEWIS ACID CHEMISTRY OF THE SULPHUR IMIDES 148

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V-1 Reactions of the Sulphur Imides with Lewis Acids

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148

148

LIST OF FIGURES

Figure Page

1-1

II -1

II-2

II 1-1

I JI-2

I II-3

111-4

1II-5

4- "The S4N4 Anion

Double Bul.b Reaction Vessel

Single Bulb Reaction Vessel with nmr Tube

31 p nmr spectra of (a) S4N4 with PCl S in a 1:1 molar

ratio, (b) S4N4 with PC1 S in a 1:3 molar rati~ ,19 '

Room temperature F nmr spectrum of "the S4N4,PFSadduct

Room temperature 31 p nmr spectrum of the S4N4·PFSadduct

First-order stick diagram illustrating the 31~ nmr

spectrum of the S4N4'PF5 adduct

Infrared spectra of the S4~'SbC1S and S4N4'PFSmolecular adducts

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45

50

51

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II 1-6 Raman spectrum of the S4N4'SbC1S adduct recorded at- 196 O'C

111-7 Proposed st~ucture of the S4N4SbC1: intermediate

I~I-8 Infrared spectra of S4N4(SbC'6)2 and· S4N4(A~F6)2'XS02

111-9 Infrared spectra of S4N4(SbF6)2 and S4N4(Sb3F,4)(SbF6)

111-10 Raman spectrum of S4N4~SbC16)2 recorqed at -196°C

111-11 Raman spectrum of S4N4(AsF6)Z"xSOZ re.corded at -196°C

~11-12 Raman spectrum of S4N4~bF6)Z recorded at -196°C

111-13 R~man spectrum of S4N4(~b3F14)(Sb~6) recorded at -t96°C

111-14 Unit cell diagram of S4N4(SbC16)z

111-15 Unit cell diagram of ~~N4(Sb3~14)(SbF6)

'IlI-16 (A) Structure of ring (A) in [S4N4][SbF6]ESbl14]"

(B) Structure of ring (B) in [S4N4][SbF6][Sb3F14]

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90

Page

(C)

(C')

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,>,Structure of ring (C) in [S4N4][SbC16J2 vieweddown the 54 axis

J. I

Structure of ring, (C) ~;ewed down the pseudo-C2axi s

111-17 Valence bond diagrams of the,s4N~+ cation

Fi gure

III-18 The Sbl14 anion, --- long contacts to neighbouringF atoms 91

IV -1

IV-2

IV-3

IV-4

IV-S

IV-6

IV-7

IV-8

IV-9

Raman spectru~ recorded at -196°C of the greenmaterial isolated from the reac'tion of S3N3Ci~ith '.SbC1 S in a 1:2 molar ratio in liquid S02

Raman spectrum of SN(S03F) recorded at -196°C

Raman spectrum a! SN(AsF6) .and other.uni~e~tified

products recorded at -196°C

Raman spectrum of SN(SbZF11 ) recorded at -196°C+ .

The SSNS ca tl on

The unit ce~l di~gram of SSNS(SbC1 6).The unit cell ~diagram of 'S4.N( SbC1 S

The mo)ecular ~uct S4N4'SbC1S

Valence Bon9 Resonance Forms for' the Molecular Adduct

S4N~'SbCls

106

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118

119

125·

lZ6

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132

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IV-10. Variation of S-N-S Bond Angle with S-N Bond Distance 138~

IV-ll Variation of N-S-N S'ond Angle with S-N Bond Distance 139'

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V-1

V-2

V-3

Proposed Reaction Sequence for the Oxidation of S7NH~nd l,4-Si N2H2 with SbC1 S

Raman spectrum of S2N(S~C16) recorded at -196°C. .The unit cell diagram of S2N(SbC16), a and bare.pa'rallel to the top and side of the page. res pec1\vel y ,

and the view is down c.

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159

162

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