Eur. Polym. J. Vol. 19. pp. 71 79. 1983 0014-3057 83/010071-09503.

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Printed in Great Britain Pergamon Press Lid

HSAB PRINCIPLE A N D D E S U L P H U R A T I O N REACTION

D U R I N G IONIC C O O R D I N A T I O N P O L Y M E R I Z A T I O N
OF THIIRANES [-1]*
A. D. ALIEV, B. A. KRENTSELand S. L. ALIEVA
Institute of Petrochemical Synthesis, U.S.S.R. Academy of Sciences, Moscow, U.S.S.R.

(Received 18 December 1981; in revisedJbrm 10 May 1982)

Abstract--Desulphuration of trimethylthiirane (TMT), catalyzed by anionic and cationic catalysts for

thiiranc polymerization, has been studied, The possibility of obtaining polymers having mono-, di- and
trisulphide bonds during TMT polymerization by typical cationic catalysts has been shown. Some
peculiarities of the desulphuration reaction during the PolYmerization of thiiranes by ionic catalysts have
been found. Differences in their catalytic action, shown by the formation of different quantities of both
disulphide --SS--bonds in polymer chain and alkene, are discussed from the point of view of HSAB
principle and symbiotic effect of ligands at the counterion. It is shown that desulphuration reactions
during the cationic and anionic polymerization of thiiranes have a similar electronic nature, consisting of
increase of coordinative state and the activation of the acceptor orbital of the thiirane sulphur atom. The
nucleophilic attack by thiirane (during cationic polymerization) or growing thiolate-ion (during anionic
polymerization) on the electrophilic sulphur atom of thiiranium intermediates

S--R or ~S + a--~ Li(AI, Znl

respectively, is accompanied by concerted fragmentation of these intermediates, giving the alkene and
disulphide fragment. Possible mechanisms have been suggested for thiirane desulphuration and
~SS-bond formation in products of the ionic polymerization of thiiranes. HSAB principle proved to be
very useful for discussion of experimental results and other aspects of thiirane polymerization.

INTRODUCTION larity changes E111 but not by the possible presence of

The practical significance of the desulphuration reac-
tion of thiiranes is usually limited by stereospecific
syntheses of alkenes [2]. We have extended the appli-
cability of this reaction by synthesis of chiral thiiranes
in the asymmetric desulphuration of their racemates
[3, 41, and by preparation of disulphide or trisulphide
polymers with uniform repeating units in the polym-
erization of thiiranes by lithium alcoholates [-5, 6] or
by their complexes with lithium alkyls or thiolates
[-7, 81. The formation of 1,2,5-trithiepanes during the
cationic polymerization of thiiranes [-91 also should
be connected with realization of desulphuration reac-
tion.
Despite numerous examples of the desulphuration
of thiiranes during their syntheses and chemical trans-
formations [21, until recently no detailed attention
was paid to the problem of realization of this reaction
in the polymerization of thiiranes, For this reason,
differences in structure and properties of polythiiranes,
obtained with different catalytic systems, were either
not discussed [10] or were explained by stereoregu-
* I. (a) In the polymerisation of thiiranes and cationic
cleawtge of polythiiranes, accompanied by alkene forma-
tion, the term "thiirane dealkenylation'" would be more
appropriate. However, we use a more usual term "thiirane
desulphuration" because this reaction is well known [2]:
(bj The present study was reported at the Soviet*Polish
Microsymposium General Peculiarities of the Ionic Polym-
erization of Heterocyclic Monomers, Moscow (September
1981).
71
di- or polysulphide bonds in polymers.
Since the known data on thiirane desulphuration
reactions do not provide enough information on the
nature of this phenomenon [21, we studied this reac-
tion during ionic polymerization of thiranes. These
data are useful for understanding the mechanism of
thiirane desulphuration, and necessary for a proper
choice of catalytic systems and optimum polymeriz-
ation conditions for the selective synthesis of mono-,
di- or trisulphide polymers having uniform structure.
EXPERIMENTAL
Trimethylthiirane (TMT) was obtained from trimethy-
loxirane and potassium thiocyanate 1-12]: b.p. 106-108";
5Y/100 tort; d~,5 0.8842; n~5 1.4644. These constants, dif-
fering from the conventional for TMT (b.p. 145-150°; d o
0.927 [13] }, are in good accordance with those of members
of the homologous series of methyl-substituted thiiranes.
TMT was identified by GLC, elemental analysis, u.v.-, i.r.-
and PMR-spectroscopy. Before use, it was dried over
Call2 and condensed into reaction ampoules.
Catalysts n-BuLi [7], ZnEt 2 [7], CdEt2 [14], BF~Et20
[7] and thiolates of zinc, cadmium and mercury [15] were
purified by known procedures. Vacuum technique and
argon atmosphere were used to avoid contamination by
moisture and air during use and/or modification of cata-
lysts. Catalyst modification was performed according to
reported procedures [7, 8] directly in reaction ampoules in
compliance with the component mole ratios indicated in
the tables.
Solvents were purified and stored over suitable drying
agents in calibrated vessels connected to the vacuum line.
72 A.D. ALIEVet al.
T M T desulphuration and polymerization were carried out
in sealed ampoules, previously heated and degassed
(10-4 torr) under conditions excluding moisture and air.
After reaction, the mixture was analysed by GLC to deter-
mine the formed alkene and unreacted TMT. The reaction
mixture was then treated with methanolic NaOH after
which all volatile materials were removed by vacuum evap-
oration (10-2torr). The dry residue was triturated and
decanted repeatedly with methanol to remove low molecu-
lar-weight fractions which were not studied since they are
not uniform products and the yield is not more than 20~o.
After drying in vacuo, fractions insoluble in methanol are
semi-solid, pale-yellow polymeric products, having intrinsic
viscosity [r/] = 0.04-0.07 g/dl (measured in benzene at 25°).
PMR-spectra were obtained with a Varian T-60 spec-
trometer at 35° in CC14 (I0~ concentration). Chemical
shifts were measured with TMS as internal standard.
RESULTS AND DISCUSSION
I. Thiirane desulphuration durin9 anionic polymeriz-
ation
It is known [6-8, 15] that the desulphuration of
thiiranes by step-by-step generated growing lithium
thiolate is an important stage of disulphide (scheme a)
and trisulphide (scheme b) polymer formation in the
polymerization of thiiranes by lithium alcoholates:
[---]-]
-C-C-S
LIOR
. . . . . "-
_~ CI- C -IS S
2n
I I
LiOR
3n -C-C-S "~
I I
This reaction was unexpected because the data on
thiirane desulphuration by metal thiolates, which are
active agents both in ring-opening [2] and in poly-
merization [16] of thiiranes, are absent. However,
investigation of data on the polymerization of thiir-
anes and the structure of polythiiranes reveals that
under certain conditions other catalytic systems also
cause the thiirane desulphuration. Thus, in polar or
even in weakly polar media and also in the presence
of electron donor additives (amines etc.), the methyl-
thiirane (MT) polymerization by various catalytic sys-
tems yields only the poly-(methylthiirane) (poly-MT)
without formation of propylene and --SS---bonds in
the polymer chain. However, in bulk or in nonpolar
media, lithium alcoholates and their complexes with
lithium alkyls and thiolates give MT polymers con-
taining up to 100~ of --SS---bonds [-5,7, 8] ; alumin-
ium alkyls yield MT polymers having not more than
70~ of--SS---bonds [17-19], and in the presence of
zinc alcoholates [15] and thiolates [20] the quantity
of--SS---bonds in polymers reaches only 20~. Cad-
mium alcoholates and thiolates under various polym-
erization conditions do not cause the MT desulphura-
tion [21]. Thus, the thiirane desulphuration and the
formation o f - - S S - - b o n d s in polythiiranes depend
not only on polymerization conditions [5-8] but also
on the nature of the metal of the catalytic system.
The considerable influence of the nature of the
metal and reaction medium, indicating the coordin-
ation mechanism of thiirane desulphuration, can be
explained by change in degree of the coordination
binding of thiirane with different metal ions. This is in
accordance with the facts that the MT desulphuration
completely stops and the poly-MT stereoregularity
reduced in the MT polymerization by organolithium
and organozinc catalysts in THF or in the presence of
amines. However, cadmium catalysts, which do not
cause the MT desulphuration under various con-
ditions, yield the stereoregular poly-MT not only in
THF but also in the presence of amines.
These data indicate the existence of other reasons
responsible for desulphuration during thiirane polym-
erization by different catalytic systems.
We examined the TMT desulphuration to examine
the possibilities for thiirane desulphuration by differ-
ent catalytic systems and to establish the real reasons
for the unique action of organolithium catalysts in the
MT polymerization [5-8]. TMT was chosen because
of its lesser tendency to anionic polymerization and
the relative ease of quantitative GLC analysis of its
desulphuration product 2-methyl-butene-2.
Table 1 shows that, similar to MT [8, 17, 20], in the
case of TMT the desulphurating ability of active
centres of the type ~ R S Me + ( ~ RS- -- the grow-
ing thiolate-ion; Me+ = the metal ion) also increases
~n + n
",,C= / (a)
I I I C\
.2,,c.c,, (b)
I I An
in the order of rig 2+ _~ Cd 2+ ,~ Zn 2+ < A13+ < Li +
and depends on the symbiotic action of anions and
donor ligands surrounding the metal ion.
It seems that the electronic structure of thiirane [2]
during coordination with various metal atoms of the
growing ion pair changed insufficiently. It is exhibited
in different behaviour of heterocycle-thiiranes which
either are selectively desulphurated or take part in the
ring-opening reaction. Noting a possible involvement
of the 3d-orbital of the thiirane sulphur atom in the
complexation with some metal ions (Hg 2+ and C d 2 +)
and also probable differences in the stability and
tightness of the formed metal-thiirane ("acid-base')
complexes, the order of Hg 2+ "-~ Cd 2+ ~ Zn 2+ <
A13+ < Li + can be explained in terms of the HSAB
principle, i.e. "hard acids (HA) preferentially combine
or form complexes with hard bases (HB), and soft
acids (SA) with soft bases (SB)" [22].
Data on the MT polymerization and TMT desul-
phuration by different catalytic systems suggest that
desulphuration is improbable if thiiranes (SB) are
coordinated with Hg 2+ and Cd 2+ ions (SA). In this
case, together with the ordinary coordination bond,
a dative d~-bond can be generated by d-electron
transfer from lower occupied d-orbitals of Hg 2+ and
Cd 2 ÷ to the vacant 3d-orbital of the thiirane sulphur
atom, which is a more efficient d~-electron acceptor
than sulphur atoms in ~ RS anion and thiol [23].
Such double-bonding intensifies the nucleophilic
 Ionic coordination polymerization of thiiranes 73

Table I. The desulphuration of trimethylthiirane (TMT) in the presence of various catalytic

systems [21]*++

TMT Alkene
Exp. TMT/Cat Time conversion yield
No. Catalyst (mole ratio) (hr) ('~;i) (o~,)

43 BuLi. LiOR* 10 96 57 33
34 BuLl. LiOR* 20 96 50 28
37 AIEt3 + R*OH 20 96 43 25
36 AIEt3 + R*OH 20 192 ~2 56
41 ZnEt2 + 2R*OH 10 96 72 57
35 ZnEt 2 + 2R*OH 20 96 41 23
50 ZnEt 2 + 2R*OH 20 192 70 42
6 ZnEt 2 + 2R*OH 50 192 40 28
18 ZnEt 2 + R*OH 50 192 89 53
309 ZnEt 2 50 192 39 21
82 [n-C6H 13S)2Zn l0 96 29 13
83 (n-C6H 13S)2Zn 20 192 35 21
29 (CH2~CH--CH2S)aZn 20 192 49 39
85 (CH2~CH--CH2 S)zCd 10 96 22
55 (CH2~CH--CHzS)zCd 20 192 30 -
108 CdEt 2 + 2R*OH 25 336 6
84 (n-C6H13S)2Cd 10 96 16 -
74 (n -- C6H13S)zCd 20 96 6
72 (CH2~------CH--CHzS)zHg 10 96 19
73 (CHz=CH--CH2St2Hg 20 96 8

* Solvent toluene, toluene TMT = 5:1 (v:v), at room temperature, R*OH-( - ) menthol.
~ The desulphuration was carried out at 0 .
+ 21 .Zh. Zhumabaev, Dissertation, Moscow ( 1981).

character of thiirane sulphur atom, as the vacant
3d-orbital of the sulphur atom is filled by d-electrons
of Hg- and Cd-counter cations. This prevents the
thiirane desulphuration because it makes it imposs-
ible for ~ RS anion (SB) to attack a nucleophilic
thiirane sulphur atom (SB). On the other hand, such
double-bonding leads b o t h to substantial weakening
of thiirane C - - S b o n d s and to the increase of the posi-
tive charge of the metal ion, which facilitate ring-
opening of thiirane by ~ R S - anion:
" RS- ....... +Cd - -
The concerted mechanism of episulphurane frag-
mentation provides a real possibility for the forma-
tion of highly reactive - R S S - anion in the form of
tightly bonded ion pair - RSS , Me + or mainly the
covalently bonded form - RSSMe. This is facilitated
by the polymerization in n o n p o l a r media or in bulk
and by the nonionic character of ~ S ~ M e (Li, Zn,
A1) b o n d s (x >/ 1). The solvation of - RSSMe and
RSS-, Me + (active centres of the thiirane ring-

I I
~Rs-c-c-s-, +cd--
I I

Desulphuration is possible if thiiranes (SB) are

coordinated with Li-, A1- and Zn-counter cations
opening reaction) by thiirane molecules is ac-
{HA), which have a higher positive charge and do not
companied by selective ring-opening of thiirane with
possess easily excited outer electrons. Such coordin-
the simultaneous formation of disulphide fragments
ation, not involving the vacant 3d-orbital of the sul-
and active centres of thiirane desulphuration reaction
phur atom, activates acceptor properties of the thiir-
of type
ane sulphur atom. In this case attack by - R S -
anion (SB) on the electrophilic thiirane sulphur atom
(SA) becomes possible. The formed transition state of R S S - - C - - C - - S - , Me" [8].
episulphurane type A, as in the thiirane desulphura-
tion by lithium alkyls [24], undergoes fragmentation
L q
by a concerted mechanism with the formation of
alkene and - RSSMe:

NRS-- Li + I" RS_ ~ Li

,,C ~ S Q / c 7 - - - " "c//\c/,,

~ S "" ---'4" ~RSSLi + C C

/ \ A
74 A. D. ALIEVet al.
Indeed, as distinct from ~ RS- anion, the ~ RSS-
anion should be more reactive and highly nucleophi-
lic in the thiirane ring-opening reactions due to the
u-effect of the heteroatom [8, 25] and the fact that one
cannot take a conformation (~G~= 90°) with a lesser
overlapping of p-orbitals of unshared electrons of ad-
jacent sulphur atoms [35].
Actually, the electronic structure of ~ RSS anion
can be stabilized only by the formation of a-bonded
disulphide fragments of type
I I
~ RSS---C--C--S-, Me +,
I I
which can take a stable conformation with the di-
hedral angle of ~ R - - S - - S - - R ~ bonds equal to ca.
oJss = 90 °.
Such an explanation agrees with the facts [5, 8]
that polymerization conditions and other factors
(basicity, polarizability and a-effect [25]) resulting in
increase of nucleophilic reactivity of the active species
( ~ RSLi or ~RSSLi) of the growing catalytic
complex ( ~RSxLi'LiOR*; x = 1 or 2) are not favour-
able for the MT desulphuration, but favour ring-
opening reactions of MT [5, 8]. Indeed, in polar
media (THF and dioxane) or in the presence of amine
additives, the formation of episulphurane inter-
mediate A is impossible since thiiranes (SB), unlike
ethers and amines (HB), have a smaller tendency to
coordinate with Li-, Zn- and Al-counter cations (HA).
(HA).
High nucleophilic reactivity of ~ RSS- anion in
the thiirane ring-opening reaction (a-effect hetero-
atom) suggest that the thiirane desulphuration by
active species of the type ~ RSMe is a rate determin-
ing stage for thiirane polymerization in processes of
disulphide [7, 8] and trisulphide [6] polymer forma-
tion. This is confirmed by the low content of mono-
sulphide units in the polymer chain and by the high
selectivity of disulphide polymer formation at differ-
ent MT conversions [7, 8].
The concerted mechanism of episulphurane frag-
mentation accounts for high stereospecificity [2,24]
and enantioselectivity [3,4] of thiirane desulphura-
tion in the presence of nucleophilic agents.
The HSAB principle also explains a number of ex-
perimental results on the stereospecific and asym-
metric thiirane polymerizations by anionic coordin-
ation catalysts. Quite a characteristic phenomenon is
the symbiotic effect of soft and hard ligands (anions
and donor molecules) at the metal ion. The symbiosis
phenomenon comprises the following concepts [22]:
(a) the surrounding of the metal ion by hard or soft
ligands increases, respectively, its "hardness" or "soft-
ness", and (b) the presence of hard or soft ligand(s) at
the metal ion facilitates the incorporation of anal-
ogous ligands into its coordination sphere. Thus, in
the absence of hard donor ligands -LiOR*
[Li+~{HA), and R*O --l-menthoxy group (HB)],
the growing active species of type ~ RS-, Li + possess
an insignificant desulphuration ability [8]. The hard-
ness of Li + counter cation in ~ RS-, Li + increased
only after the addition of hard LiOR* molecules with
the result that the thiirane desulphuration by the
mixed complexes of type ~ RSLi.xLiOR* (x >~ 1)
became possible [8].
The symbiosis phenomenon also allows explana-
tion of:
(1) the shift to the right of the equilibrium:
(~RSLi), + (LiOR*),, ~ ~RSLi.xLiOR* (m 7> n);
the preferential formation and catalytic action of
mixed complexes, even if x = 1 (when m = n), are con-
firmed by the selective formation of disulphide poly-
mers on the complex system ~RSLi.LiOR*, despite
a higher rate of the MT polymerization by thiolates of
lithium ~ RSLi in the absence of LiOR* [8];
(2) the higher content of--SS---bonds in MT poly-
mers, obtained by the use of Zn(OR*)2 [15], than in
the presence of Z n ( S C H z - - C H ~ - - - C H z ) z [20] (R*O-
is HB, while CH2~--~-CH--CH2S anion is SB);
(3) the decrease of MT desulphuration rate and
even the stopping of propylene evolution with in-
crease of MT conversion by use of Zn(OR*)z [151
and iso-BuaAl [16], which can be caused by the par-
ticipation of hard R*O- and R anions in initiation
steps. This leads to the surrounding of metal ion by
more soft ~ R S - anions:
Zn(OR*)z MT , ~ R S - , +ZnOR* Mr , ( ~ R S h Z n .
A low enantioselectivity of MT asymmetric poly-
merization on the system CdEt z + chiral alcohol or
diol, as compared to the corresponding organozinc
catalysts [26], may be explained by a faster trans-
formation of Cd(OR*) 2 to Cd(SR ~)2, as a soft metal
ion (Cd 2+) is more strongly bonded with soft ligands.
On the other hand, the high stereoregularity of
poly-MT, prepared by cadmium catalysts even in
polar media such as THF (HB) or in the presence of
hard donor additives (tertiary amines, ethers, etc), is
determined by the tendency of the soft cadmium ion
(SA) to coordinate preferentially soft electron donors
(thiiranes and sulphur atoms of the growing polymer
chain). Under the same conditions, organozinc cata-
lysts yield amorphous polymers, because the hard
zinc ion (HA) coordinates more preferentially hard
ligands--THF and amines (HB) [26]. The increase of
poly-MT stereoregularity with the enhancing of soft-
ness of Me + counter cations in metal thiolates
(Li + < AI3+ < Zn 2+ ~ Cd 2+) can be explained by a
more stable coordination of the soft metal ion (SA)
with thiiranes and/or with sulphur atoms (SB) of
growing polymer chain.
It is known that the softness of transition metal
ions increases with decrease of their oxidative state,
which is stabilized by surrounding of the metal ion by
soft ligands. Thus, the observed formation of more
soft Cu ÷ ions, which is accompanied by a colour
change of the reaction mixture [27] and the appear-
ance of a bend in the MT conversion curve [16] dur-
ing MT polymerization by the Cu 2+ acetylacctonate
[27] and Cu(SR)2 [16], could be related to the poss-
ible redox reaction:
( ~ R S ) 2 C u ~ ~RSCu + ~RSSR
 Ionic coordination polymerization of thiiranes 75

2. Thiirane desulphuration during cationic polymeriz-
ation
The thiirane desulphuration is also caused by
various electrophilic reagents; the mechanism remains
unclear [2].
The formation of alkene and disulphide compounds
was also observed during cationic polymerization of
tbiiranes [9, 17-19]. For instance, in the presence of
typical cationic catalysts (Et30+BF~, etc.) thiiranes
and their polymers are transformed into 1,2,5-trithie-
panes according to the scheme [9]:

"R
] ~R

+ \C=C- + S S

MT polymerization by aluminium alkyls [17-19] [17-19], yields polymers with increased content of
and their water modifications [19], which are sup- - - S S - - b o n d s (up to 70~o [18]) by the scheme [19]:
posed to act according to the cationic mechanism

,___(, s-A1c, I
S,. / + C H 2 = CH +

CHs Xs/
CHs

These schemes show that an alkene is formed as a
result of polymer chain cleavage, but not by the thiir-
ane desulphuration (or the thiiranium ion dealkenyla-
tion). However, true reasons exist for the thiiranium
ion dealkenylation that are responsible for the forma-
tion o f - - S S - - b o n d s in polymer chain or 1,2,5-trithie-
panes in the thiirane polymerization and/or polythiir-
ane cleavage by typical cationic catalysts. This is
facilitated by a greater probability of formation of
thiiranium intermediate in the thiirane electrophilic
reactions [2] and the thiiranium nature of active spe-
cies in the cationic polymerization of thiiranes [28],
in accordance with the calculated data, showing a
higher stability of thiiranium ions than the corre-
sponding open-chain cationic intermediate by ca. 50
kcal/mol [30].
Indeed, the ambident behaviour of thiiranium salts,
caused by the presence of electrophilic centres of the
two types (at carbon atoms and at sulphur atom
[29, 30]) makes more probable the alternative possi-
bility of alkene formation not only in the cationic
polymerization of th'iiranes (path "a"), but also in the
cationic cleavage of polythiiranes (path "b");

S
sL. s

)__s + ,',R- S ~ L .
76 A. D. ALIEVet al.
According to this simplified and general scheme,
the positively charged thiiranium sulphur atom (SA)
is subject to nucleophilic attack by soft bases--the
thiirane (attack "a" in the case o f - - S S - - b o n d forma-
tion in polymers) or the sulphur atom of growing
polymer chain (attack "b" in the case of 1,2,5-trithie-
pane formation). Such reaction paths, accompanied
by alkene evolution, are realized due to a higher con-
centration of cationic charge at the thiiranium sul-
phur atom, achieved in its most favourable sp 3- and
p-configurations [29, 30].
The proposed mechanism of thiirane dealkenyla-
tion is consistent with the fact that the reaction of
cyclooctene-S-methylepisulphonium 2,4,6-trinitroben-
zene sulphonate with a variety of nucleophiles occurs
more often by attack at sulphur than at carbon [29].
Data on chlormethylthiirane and 3-chlorthietane
interaction with some nucleophiles [31] also suggest
the possibility of thiirane desulphuration and disul-
phide fragment formation during cationic polymeriz-
ation of thiiranes in the above scheme:
(a)RO-K +
I A
Hard bases R O - attack the "harder" electrophilic
centre (CH +) of bicyclic thiiranium ion 1 (path "a'),
whereas soft bases of type R'S- change the reaction
path, attacking the "softer" electrophilic centres
of ion I (path "b"). The increase of the softness of
the nucleophilic agents R'S- in the order
(EtO)zP(S)S- < PhS- < BuS- leads to higher yield
of compound B: A/B = 100/0; 50/50; 5/95, respect-
ively. Compound B is a peculiar product of bicyclic
ion I dealkenylation. These data lead to ranking the
R3S ÷ ion in the following order of the softness de-
crease of soft organic cations (SA) [22]:
HS + > RS + > CH~ > RCH~" /> R3 s+
> R2CH + > R3C ÷ > Ph +
which allows us to predict the reaction path (ring-
opening or dealkenylation of thiiranium cycle) or to
change the latter by the choice of conditions for the
cationic polymerization of thiiranes.
To a first approximation, the thiirane desulphura-
tion reaction during cationic polymerization can be
considered as a reversible reaction between alkylsul-
phenyl salts ~RS+An - and alkenes (SB) [2,30],
complicated by the presence of the softer base--thiir-
ane:
~RS + A n + ~C=C~ l,
An-
~RSS
lI!
+ ~C--C x
Evidently, factors facilitating the formation of
stable thiiranium salts I (the tightness of ion pair, the
increase of steric effects at ring C-C bond, low reac-
tion temperature and nonpolar media [2]) rather than
the reaction product 1I, should also favour the desul-
phuration (path "a") in electrophilic transformations
of thiiranes by this scheme. Actually, a hypothetical
RS + ion, which can be generated in the transition
state of concerted dealkenylation of growing ion pair
I, is a softer acid than the thiiranium ion 1, R3 S+ ion
and carbocations, and the thiirane is a softer base
than an alkene. Therefore, in corresponding reaction
conditions, the desulphuration and the formation of
disulphide fragments in the cationic polymerization of
thiiranes would be a rule rather than an exception.
This follows also from experimental data on the ca-
tionic polymerization of thiiranes [9, lib, 17-19, 32] if
these data are considered from the view point of the
proposed concept and general scheme for the cationic
/ ~ RO- ( H B ) = H O . PhO. RCO0-
/ i I
+ R' SS ---J
B
polymerization of thiiranes and cationic cleavage of
polythiiranes.
Based on the proposed general scheme and the
above order of soft organic cations, it can be assumed
that the probability of desulphuration by path "a"
with the formation of the growing alkylthiothiiranium
ion Ill, would increase only at certain acid-base ratios
of thiirane and components of the growing ion pair |.
For example, the dealkenylation by path "a" can take
place if the thiiranium sulphur atom has a greater
softness than thiiranium carbon atoms (obtained in
the polymerization of more substituted thiiranes), and
the counter anion An is HB. In this case the prefer-
ential ion-pairing between the hard counter anion
A n - and relatively hard thiiranium carbon atoms
( ~- C + and /" CH +) promotes the nucleophilic attack
by the thiirane (SB) on a more accessible and un-
screened (by A n - ) sulphur atom (SA) of the thiira-
nium ion.
Steric and electronic factors should be unfavour-
able for the dealkenylation by path "a", if the hard
counter anion An- (HB) is disposed mainly at the
~An
~ RS~-@*"]'" An- 4 l, ~RS_..A//
11
&
 Ionic coordination polymerization of thiiranes 77

relatively hard thiiranium sulphur atom. The latter

can form in the polymerization of less substituted
thiiranes (thiirane, MT, 2,2-dimethylthiirane, etc.). In
this case the increase of the relative softness of thiira-
nium carbon atom(s) (+CH2 is a more SA, than
R3 S+) promotes the reaction path "b" due to the
preferential attack by thiirane (SB) on the thiiranium
carbon atom(s) (SA).
Thus, the probability of electrophilic desulphura-
tion during polymerization of more substituted thiir-
e~
anes (TMT, 2,3-dimethylthiiranes, etc.) should in-
crease by use of catalysts generating the hard counter
anions An-. Such probability in the case of less sub-
stituted thiiranes (thiirane, MT, 2,2-dimethylthiirane,
"2
etc.) can increase by the generation of the soft counter
d =
anion An-. This is confirmed by the comparison of t'--

data on the cationic polymerization of MT and TMT

.- m
by typical cationic catalysts, BF3'Et20 and
BF3"R*OH, generating the hard counter anions
[BF3OEt]-, BF2 and [BF3OR*] .
It turned out that, under the same conditions, only
a more substituted and basic TMT yields polymers
having the increased sulphur content (Table 2). The
calculated value of the sulphur content for the mono-
sulphide TMT polymers is 31.377o. It is achieved only t-
o
in the polymerization of TMT by organocadmium
catalysts, which do not cause the thiirane desulphura- g
tion [21].
The larger basicity of TMT in comparison with MT
O
follows from the much greater OD-i.r.-bandshift of
CH3OD in TMT (Yon= 2542cm- 1) and MT
(yon= 2599cm *t. Hence, the relative basicity of
TMT and MT, determined by difference of Yon values 2~
in CCl~(vo~ = 2689cm ~) and base [7], is equal to
Avon = 147cm ~ and 90cm ~, respectively. It is con-
sistent with the bathochromic shift of u.v.-absorption
maximum in the series thiirane (261nm), MT
0
(262.4 nm) and TMT (263 nm) [21]. Apparently, the
o
inductive effect of methyl groups in TMT favours the
increase of electron density at the sulphur atom.
Thus, the greater basicity of TMT, the relative soft-
ness of the sulphur atom in the growing thiiranium
0
ion, the generation of hard counter anion, and also
the significant steric hindrances for the TMT attack
by path "%" facilitate the thiirane desulphuration and
r.i
the formation of polymers with a high sulphur con-
e~
tent during cationic polymerization of TMT.
The presence of trisulphide (-SSS-) bonds in TMT
polymers confirms the strong influence of steric
factors on the preference for the nucleophilic attack
by thiirane in concurrent reaction paths "a" and "b".
Indeed, the transformation of thiiranium ion I into
II ,,.a ~ o
thiothiiranium ion Iii should not favour the following m m m
dealkenylation of III due to the probable decrease of
the positive charge on the sulphur atom of cyclic ion ¢3 O

III. ,~+
Data on the microstructure of TMT polymers,
~z ~
given in Table 2, were obtained by comparison of
* ~ ++ II
PMR-spectra and microanalyses of polymers, which
are correlated with i.r.- and u.v.-data. These data are
also in satisfactory agreement with those of copoly-
mers of TMT and cyclic-Ss, obtained by study of their
PMR-, i.r.- and u.v.-spectra [21,33]. In particular,
microanalyses in combination with determination of
the average chemical shift (5~,.) of CH-S,-proton sig-
nals in PMR-spectra of polymers give reliable
78
information on the average number of adjacent sul-
phur atoms "x" in polymers of the type
[CH(CH3)C(CHa)2-Sx] n [21, 33].
The broadening of CH-Sx-proton signals (Fig. 1),
observed even at the same sulphur composition
(x ~ 2 and 6,v = 3.21ppm) of cationic polymers
(exps. 89 and 151, Table 2), indicate that polymers
consist of differing ratio of mono-, di- and trisulphide
units, and not only disulphide units.
This is confirmed by the PMR-spectra analysis of
methyl protons peaks which are split only when the
structural uniformity of polymers changed, since
methyl protons are stereoinsensitive like those of
mono- and disulphide polymers from MT [8, 343, and
the position of their signals does not depend on the
molecular weight of polymers (at least for n > 5). In
the case of monosulphide polymers of TMT, obtained
by cadmium catalysts, methyl protons are displayed
as two singlet signals of non-equivalent gem-dimethyl
groups (due to the presence of chiral centre) at
= 1.26 ppm and 1.48 ppm, and also the doublet sig-
nal of CH3-CH-group at ~ = 1.50 ppm (Fig. 1). The
/'11 I of acceptor orbital of thiirane sulphur atom under
I I
4.0 3.0 2.0 i.o
~, ppm
Fig. 1. PMR-spectra (in CC14) of trimethylthiirane poly-
mers, obtained by cationic catalysts (2, 3, and _4--exps 89,
151 and 9 in Table 2, respectively) and on
Cd(SCHzCH=CH2)2 (1--exp. 55 ill Table 1).
A. D. ALIEVet al.
intensity ratio of CH3-peaks at 1.26ppm and
(1.48 + 1.50) ppm is c a , 1:2.
Thus, the downfield shift of the sharper and less
intensive signal at 1.26 ppm (when polymers with uni-
form structure are formed) or the appearance of ad-
ditional peaks in this spectral region [observed in
PMR-spectra of polymers, obtained by cationic cata-
lysts (Fig. 1)], should be related to an increase of the
polysulphidity degree "x" of the polymer chain.
Actually, less intense and narrow peaks of methyl
protons at 1.26, 1.32 and 1.37 ppm, observed in spec-
tra of polymers with high sulphur content, should be
attributed to polymer chain fragments with mono-,
di- and trisulphide bonds, respectively. This is con-
firmed by the noticeable downfield shift of CH-Sx-
protons with increase of sulphur content in polymers
(Fig. 1) and agreed with the microanalytical data for
polymers (Table 2). Insignificant downfield shift of
other methyl proton signals (from 6~v = 1.49 ppm for
x = 1 to 6,v = 1.52 ppm for x = 3) prevents this spec-
tral region from being used for the determination of
"x" in TMT polymers.
Data on the polymer microstructure, given in Table
2 and obtained by estimation of the relative intensity
(mainly by height) of peaks at 1.26, 1.32 and 1.37 ppm,
are approximate.
The propylene evolution and the formation of
--SS---bonds in MT polymers may be possible only
with cationic catalysts, generating a less hard counter
anion An-, than [BF3OR ] - or BF2. The formation
of disulphide polymers (up to 70~o of - - S g - - b o n d s )
during MT polymerization on such cationic catalysts
as iso-Bu3A1 [17, 18], Et3A1 and its water modifica-
tions [19], and also some complexes of PdC12 and
PtCI2 [32], supports and above supposition.
The proposed scheme for the thiirane electrophilic
desulphuration enable us to explain also the preferen-
tial formation of polymer chain with alternating
--S--- and --SS--- units [19].
Thus, the electronic nature of the formation of tran-
sition state of episulphurane type and thiiranium
intermediates is essentially the same because of the
enhancement of coordinative state and the activation
certain conditions of the anionic and cationic polym-
erization of thiiranes. Nucleophilic and electrophilic
desulphuration of thiiranes are facilitated under con-
ditions (nonpolar reaction media, low reaction tem-
perature, etc.) leading to the formation of episulphur-
ane and thiiranium intermediates in covalent form or
in the form of tightly bonded ion pair. The ambident
behaviour of these intermediates, the dual reactivity
of which depends on the nature of monomer, reaction
medium and the counterion of growing polymer
chain, requires careful choice of catalytic systems and
polymerization conditions. Solution of this problem is
possible by the predicting character of the HSAB
principle and symbiosis phenomenon. The HSAB
principle allows an explanation, at present qualitative
but later perhaps quantitative 1-35], of the reasons for
o selectivity of acid-base reactants in concurrent desul-
phuration and ring-opening reactions of thiiranes
during ionic coordination polymerization. The sym-
biosis phenomenon allows choice of the optimum
conditions and to establish suitable acid-base ratios of
thiirane and components of the growing ion pair for
 Ionic coordination polymerization of thiiranes
the selective direction of reaction by path, leading to
the f o r m a t i o n o f p o l y m e r s with required structure and
properties.
T h e present data s h o w that the H S A B principle,
widely used in organic, o r g a n o - m e t a l l i c and coordin-
ation c h e m i s t r y [22], can be useful also for m a c r o -
molecular chemistry, a n d in particular for the syste-
m a t i z a t i o n o f e x p e r i m e n t a l data a n d the discussion of
various aspects of the ionic c o o r d i n a t i o n polymeriz-
ation (the influence of the nature o f m o n o m e r , cata-
lyst, etc. a n d also the character of reaction media and
various additives on the stereoregularity and unifor-
mity of the p o l y m e r chain).
.4cknowled{tements We thank Dr Zh. Zhumabaev for par-
ticipation in the experimental work and Dr A. Yu, Koshev-
nik for measurcments of PMR-spectra.
REFERENCES
I. (a) In the polymerization of thiiranes and cationic clea-
vage of polythiiranes, accompanied by alkene forma-
tion, the term "'thiirane dealkenylation" would be more
appropriate. However, we use a more usual term
"~thiirane desulphuration" because this reaction is well
known [_2]; (b) The present study was reported at the
Soviet-Polish Microsymposium General Peculiarities o{
the Ionic Polymerization <,~]'Heterocyclic Monomers.
Moscow September (1981).
2. A. V. Fokin and A. F. Kolomiets, Khimia Thiiranov,
Chapter 10. Nauka, Moscow (1978).
3. A. D. Alley, I. P. Solomatina and B. A. Krentsel,
Chemical Tram;[brmations of Polymers (preprints),
I U P A C International Conference, Vol. 3, Part 60, pp.
I 11. Bratislava (1971).
4. A. D. Alley, I. P. Solomatina and B. A. Krentsel, Mac-
romolecules 6, 797 (1973).
5. A. D. Alley, F. D. Gasanov and T. K. Khanmamedov,
Azerh. Khim. Zh. 5, 72 (1978).
6. A. D. Alley, A. Yu. Koshevnik and F. D. Gasanov,
l,)'sokomo/ck. Soedin. A21, 1340 (1979).
7. A. D. Alley, B. A. Krentsel, G. M. Mamediarov, I. P.
Solomatina and E. P. Tiurina, Kinetics and Mechanism
~[ Polyreactions (preprints), I U P A C International Sym-
posium on Macromolecular Chemistry, Vol. 2, p. 353.
Budapest (1969); See also Eur. Polym. J. 7, 1721 (1971).
8. A. D. Alley, I. P. Solomatina, A. Yu. Koshevnik, Zh.
Zhumabaev and B. A. Krentsel, ~)'sokomolek. Soedi~l.
A19, 173 (1977).
9. E. J. Goethals, Adv. Polym. Sci. 23, 103 (1977).
79
10. H. Ito, S. Sakai and Y. lshii, J. chem. Sot., Japan, lint.
Chem. Soc. 71,288 (1968).
11. (a) S. Adamek, B. B. Wood and R. T. Woodhams, Rub-
her Plast. A~/e 46, 55 (1965); (b) E. J. Vandenberg. J.
Polym. Sci. A-l, 10, 329 (1972).
12. Zh. Zhumabaev, A. D. Aliev and B. A. Krentsel. Khim.
yeterotsik, soedin. 6, 854 (1974).
13. C. Galingaert. Bull. Soe. Chim., Bel,qique 31, 109 (1922).
14. H. Krause, Ber. 50(11), 1813 (1917).
15. I. P. Solom~ltina, E. P. Tiurina, A. D. Alley and B. A.
Krentsel, Physiolo~/ically and Optically Active Polynler
Compout~ds, Proceedings of II All-Union Symposium
(October 1968), pp. IO 23. Zinatne, Riga (1971).
16. R. T. Wragg, J. chem. Soc. Part C, 2087 (1969).
17. T. N. Kazanskaya, Dissertation, Moscow (1975).
18. T. N. Kazansk~lya, D, E. Ilyina and B. A. Krentsel,
L~vsokomolek. Soedin. AI5, 2300 (1973).
19. P. Dumas, N. Spassky and P. Sigwalt. J. l'olym. Sci.,
Polym. Chem. Ed. 14, 1015 (1976).
20. W. Cooper, Br. Po/ym. J. 3, 28 (1971).
2 I. Zh. Zhumabaev, Dissertation, Moscow ( 1981 ).
22. R. G. Pearson and I. Songstad, J. Anl. chem. Soc. 89,
1827 (1967): R. G. Pearson, J. Chenl. Fd, 45, 581, 643
(1968).
23. R. J. P. Williams, Amz. Reps. Pro~lr. Chem., Chem. Soc.
Lomt. 56, 87 (1959).
24. B. M. Trost and S. D. Ziman, J. oral, Chem. 38, 932
(1973).
25. J. O. Edwards and R. G. Pearson, J. Am. chem. Soc. 84,
16 (1962).
26, P. Sigwalt, Pure appl. Chem. 48, 257 (1976).
27. T, N. Kazanskaya, D. E. Ilyina, G. P. Karpatcheva and
B. A Krentsel. I/vsokamolek. Soedin. BI3, 132 (1971).
28~ L. A. Korotneva and G. P. Belonovskaya, l_'sp. Khim.
41, 150 (1972).
29. D. C. Owsley. G. K. Helmkamp and S. N. Spurlock,
J. Am. chem. Soe. 91, 3606 (1969); D. C. Owsley, G. K.
Helmkamp and M. F. Rettig, ibid. 91, 5239 (1969).
30. Y. Kikuzono, T. Yamabe, S. Nagata, H. Kato and K.
Fukui, Tetrahedron 30, 2197 (1974).
31. O. N. NouretdinowL and B. A. Arbouzov, These.s ~/the
Reports at X I I Scie~lt(fie Session on Chemistry and
"I'echnolo~ly e# Or¢lamc Compounds ~! Sulphur amt Sztl-
phur Oils, p. 151. Riga (1971).
32. P. Dumas. J. P. Girault and P. Guerin, Polym. Bull. 2,
257 (1980).
33. A. D. Alley, Zh. Zhumabaev. A. Yu. Koshevnik, S. L.
Alieva and B. A, Krentsel, .4zerh. Khim. Zh. 3, 77
(1980).
34. A. D. Alley, Zh. Zhumabaev, and B. A. Krentsel,
Nature 280, 5728, 846 (1979); A. D. Alley, S. L. Alieva
and B, A. Krentsel, ~vsokomolek. Soedin, A22, 1171
( 1980).
35. Chemical Reactivity and Reaction Paths (Edited by G.
Klopman), Chapters 4 and 5. Wiley, New York (1974).