Phosphinoyl and thiophosphinoylcarbodithioates: Synthesis, molecular structure, and application as new efficient mediators for RAFT polymerization

Article abstract of DOI:10.1002/chem.201404631

New phosphinoyl and thiophosphinoylcarbodithioates were synthesized in a one-pot reaction from the corresponding phosphinochalcogenides. Compounds of this new generation of thiocarbonylthio derivatives have been fully characterized by IR as well as ¹

Full text of DOI:10.1002/chem.201404631

DOI: 10.1002/chem.201404631
Full Paper
&
Polymerization Agents
Phosphinoyl and Thiophosphinoylcarbodithioates: Synthesis,
Molecular Structure, and Application as New Efficient Mediators
for RAFT Polymerization**
[a]
[a, c]
[a]
[b]
Stꢀphane Maziꢁres,* Ihor Kulai,
Mathias Destarac*
Roland Geagea, Sonia Ladeira, and
[a]
Abstract: New phosphinoyl and thiophosphinoylcarbodi-
thioates were synthesized in a one-pot reaction from the
corresponding phosphinochalcogenides. Compounds of this
new generation of thiocarbonylthio derivatives have been
cient reversible chain-transfer agents for the reversible addi-
tion-fragmentation chain transfer (RAFT) polymerization of
styrene (St) and n-butyl acrylate (nBA), with controlled
number-average molecular weights (M ) and narrow disper-
n
1
31
13
fully characterized by IR as well as H, P, and C NMR spec-
troscopy and by mass spectrometry. Their solid-state struc-
tures reveal that they are isostructural but crystallize in dif-
ferent space groups. These new compounds are highly effi-
sity values (ꢀ<1.3). The controlled character of the polymer-
ization was further exemplified by MALDI-TOF mass spec-
trometry and the synthesis of PSt-P(nBA) diblock copoly-
mers.
Introduction
tional steps of radical polymerization, the RAFT mechanism in-
volves two more steps (Scheme 1), in which both the starting
agent I and the generated macro-agent III should possess a re-
active C=S double bond. The intermediate radicals II and IV
should fragment rapidly in favor of the products. The R group
should give a RC radical with a stability at least comparable to
After about twenty years of intensive research on reversible
[
1]
deactivation radical polymerization (RDRP), complementary
mature synthetic strategies including atom transfer radical
[
2]
polymerization (ATRP),
nitroxide-mediated polymerization
[
3]
[4]
(
NMP), organoheteroatom-mediated polymerization, cobalt-
that of the propagating radical and a suitable reactivity for effi-
cient chain initiation, whereas the Z group dictates the rate of
addition of radicals on the C=S bond and the chain-equilibra-
[
5]
mediated radical polymerization (CoMP), and reversible addi-
[6]
tion–fragmentation chain transfer (RAFT) polymerization
[7]
[8]
allow an infinite number of options for the preparation of pre-
cisely controlled polymers in terms of molar mass, molar mass
distribution, end-functionality, and architecture. Among all
these technologies, RAFT polymerization has attracted a great
deal of attention, in particular because of its high tolerance to
functional monomers and its compatibility with waterborne
processes. The RAFT process involves the action of compounds
bearing a thiocarbonylthio function. These agents of the gen-
eral formula Z(C=S)SR control the radical polymerization of
a large spectrum of vinyl monomers. In addition to conven-
tion kinetics. The R and Z groups are then key levers in the
reactivity of these agents toward the propagating radicals and
their fragmentation rates. Consequently, for a given monomer
it appears essential to select both the appropriate radical leav-
ing R but also the Z group to properly adjust the reactivity of
the thiocarbonyl bond and the stability of the intermediate
[9]
radicals. The literature is rich in theoretical and experimen-
[10–14]
tal
studies related to the main families of RAFT agents,
which are classified by the atom which is in a position to the
[
10]
[11]
thiocarbonyl group, namely dithioesters, dithiocarbamates,
[12]
[13]
trithiocarbonates, and dithiocarbonates (or xanthates, also
[14]
[a] Dr. S. Maziꢁres, I. Kulai, Dr. R. Geagea, Prof. Dr. M. Destarac
known as MADIX agents). These four families present a Z
group linked by a carbon, a nitrogen, a sulfur or an oxygen
atom, respectively. However, the presence of phosphorus in
RAFT agents is much less described, in either Z or R groups.
A survey of the literature shows three different categories of
phosphorus-containing RAFT agents. Starting with those that
involve the phosphorus atom in the R group, phosphine
IMRCP, University of Toulouse, CNRS UMR 5623
118 Route de Narbonne, 31062 Toulouse (France)
E-mail: destarac@chimie.ups-tlse.fr
mazieres@chimie.ups-tlse.fr
[b] Dr. S. Ladeira
Institut de Chimie de Toulouse
1
18 route de Narbonne, 31062 Toulouse (France)
c] I. Kulai
Department of Chemistry, Taras Shevchenko National University of Kyiv
4/13, Volodymyrska Street, City of Kyiv, 01601 (Ukraine)
[
1 2
oxide-containing (R R P(O)À) R groups found applications for
anchoring RAFT functionalities at the inorganic surface of
6
[15,16]
quantum dots.
Moreover, phosphonate and bisphospho-
[
**] RAFT=reversible addition–fragmentation chain transfer.
nate leaving groups in xanthate RAFT agents were efficiently
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201404631.
[17]
used in RAFT polymerization of vinyl acetate. Another strat-
Chem. Eur. J. 2014, 20, 1 – 10
1
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M=W, Cr, Mo and R=ÀCH CN,
2
ÀCH(CH )C H ) as mediators for
3
6
5
the RAFT polymerization of St
[27]
and n-butyl acrylate (nBA). In
parallel, Chen et al. polymerized
St and tert-butyl acrylate by
using
tungstenpentacarbonyl
derivatives with benzyl and allyl
[28]
as leaving R groups. Our first
results confirmed that these
metallophosphorus-based com-
pounds behave as efficient RAFT
agents. It appeared that their ef-
ficiency was not altered by vary-
ing the nature of the metal
center. Interestingly, we demon-
strated that the chain-transfer re-
activity, thermal and chemical
stability of phosphino RAFT
agents and the resulting poly-
mers could be easily monitored
Scheme 1. Mechanism of the RAFT polymerization.
31
[27]
egy consisted in using similar phosphonate esters in order to
prepare an a-functional phosphonic acid polymer chain, which
gave strong chelation properties for the stabilization of iron
by P NMR spectroscopy. The next step was to study the in-
fluence of the direct environment around the phosphorus
center by using ligands providing more versatile electronic ef-
fects. We report here the synthesis and studies in radical poly-
merization of phosphinoyl and thiophosphinoylcarbodithioates
as new organophosphorus-based RAFT agents, namely P-RAFT.
[
18]
oxide nanoparticles. Lastly, phosphine and phosphine-boron
complex groups were described to allow the modification of
polymer end-groups by means of formation of a peptide
[
19]
bond, leading to biocompatible polymers. Phosphorus can
[
13]
also be part of the Z group, and Destarac et al. showed that
phosphonate associated to fluorinated group in the alkoxy Results and Discussion
part of a xanthate disfavors the conjugation of the oxygen
Synthesis and characterization of new carbodithioates
atom and enhances the reactivity of the carbonÀsulfur double
[
20]
bond, which was later confirmed by Meiser et al. by means
of EPR spectroscopy studies. Finally, a third class concerns
RAFT agents that bear a phosphorus atom at the a-position of
In the RAFT polymerization, it is well established that the reac-
tivity of the reversible transfer agent must be adapted to the
type of monomer involved. Dithioesters or trithiocarbonates
are suitable for controlling the polymerization of styrenic
monomers, acrylates, and methacrylates, also called “more-acti-
vated” monomers (MAMs), but inhibit the polymerization of
“less-activated” monomers (LAMs), such as vinyl acetate or N-
vinylpyrrolidone. In contrast, agents suitable for controlling the
polymerization of LAMs, such as dithiocarbamates and xan-
thates, tend to be ineffective with MAMs, because of the very
low rate of addition of the propagating radical to the C=S
double bond. Taking these features into consideration, Rizzar-
do and coworkers proposed a few years ago an elegant alter-
native with a reversible protonation of a dithiocarbamate,
which could lead to a switchable RAFT agent compatible with
[21]
the thiocarbonylthio group. Recently, Barner-Kowollik et al.
used the great ability of phosphonated dithioesters to under-
go hetero-Diels–Alder (HDA) cycloaddition reactions for step-
growth polymerization of difunctional monomers. But in the
RAFT polymerization, after one single example reported in
[
22]
a CSIRO patent, the first detailed studies concerned phos-
[
23,24]
phoryl and (thiophosphoryl)dithioformates
of the general
formula R-S-(C=S)-P(X)(OR’) (X=O or S). However, their behav-
2
ior in the polymerization of styrene (St), leading to an uncon-
trolled number-average molar mass (M ) values and high dis-
n
persity (ꢀ>2), was not conclusive and suggested a contribu-
[
25]
tion of side reactions. Later, Barner-Kowollik et al. generated
two low molecular mass poly(2-hydroxyethyl acrylate) poly-
mers with low dispersity (ꢀ=1.13) mediated by a 2-cyano-
prop-2-yl-(diethoxyphosphoryl)dithioformate, for click conjuga-
tion with various dienic systems. For these strategies, the same
group also reported the use of low molecular mass PSt with
low dispersity obtained from a benzyl(diethoxyphosphoryl)di-
[29]
monomers of highly disparate reactivities. Thus, they were
able to synthesize narrow dispersity poly(MAM)-block-poly-
(LAM).
As the reactivity of these universal dithiocarbamates is
linked to the mobility of the nitrogen lone pair, their phospho-
rus-based analogs may show a similar behavior. By moving
down in Group 15 we expect more switching modes. Phospho-
rus differs from nitrogen in its lower electronegativity and also
by its ability to coordinate to a wider range of substrates and
complexants to trap its lone pair. The major remaining obstacle
[
26]
thioformate.
At the beginning of our work, we first studied metallophos-
phorus-based compounds such as Group 6 metal pentacarbo-
nyldiphenyl-phosphinocarbodithioates (M(CO) PPh CS R, with
5
2
2
&
&
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[
30]
is the synthesis of a phosphinodithioester, with a phosphine
group adjacent to the thiocarbonylthio. Our alternative is to
prepare a phosphinoyl or a thiophosphinoyl RAFT agent and
later, after an initial polymerization, modify its reactivity by re-
moving or replacing the chalcogenide (oxygen or sulfur) to
give either the phosphinodithioester or another phosphorus-
based complex.
intermediate lithium dithioformate salt is detected immediately
by the appearance of a characteristic red coloration of the THF
solution. The first step of the reaction was also monitored by
31
P NMR spectroscopy and showed quantitative formation of
the intermediate prior to the final alkylation with 1-bromo-
ethylbenzene, which takes place at the sulfur atom. After work
up and purification by column chromatography, the phosphi-
noyl (1, 3) and thiophosphinoyl (2, 4) carbodithioate esters
were isolated as pink-dark red oils. Recrystallization from a di-
chloromethane/pentane mixture (1:10) led to crystalline prod-
ucts. Compounds 1–4 have a good solubility in polar and non-
polar solvents, such as pentane, toluene, or cyclohexane.
As we reviewed in the introduction, phosphorylated di-
thioesters have scarcely been described in the polymerization
literature. In organic chemistry, phosphoryl and (thiophosphor-
yl)dithioformates have not been so much studied. Only a few
articles have focused on the reactivity of the C=S bond. Some
examples, which have been related in the literature, are addi-
None of these compounds are air-sensitive in the solid state
or in solution, which is an advantageous feature for further use
in free-radical polymerization. Satisfactory spectroscopic and
analytical data of these compounds were collected. Chemical-
[
31]
tions to thiols leading to diacetal derivatives, pericyclic reac-
[
32]
tions with unsaturated systems, or radical addition, showing
[
33]
that these compounds are efficient radical traps.
The present work deals with phosphinoyl and thiophosphi-
ionization mass spectrometry (CI-MS/NH ) revealed the peak
3
1
2
+
noyl carbodithioates of the general formula R R P(X)CS R (X=
assigned to the [M+H] ion in all cases. By using electron
2
1
2
O, S; R and R =alkyl or aryl groups). These compounds have
been briefly studied by organic chemists, but never applied to
polymerization. The first reports were published by Dahl and
impact ionization mass spectrometry, fragmentation becomes
more effective with mainly cleavage of the PÀC(=S) and SÀCH
1
bonds. The H NMR spectra (Figures S-1 to S-4 in the Support-
[
30]
Larsen in the 1960s, who described the synthesis of potassi-
um phosphinodithioformate salts and six related thiophosphi-
noyldithioformates. Two other derivatives were later reported
ing Information) show characteristic deshielded signals for the
CH groups connected to the sulfur with chemical shifts in the
range from d=5.23 to 4.80 ppm. The multiplicity is a double
quartet, which confirms that this proton is correlated both to
[
34,35]
with cyclohexyl groups on the phosphorus,
and studied as
2
3
ligands to get stable h -CS-bonded platinum complexes. Con-
the methyl group in the a-position ( J(H,H)=7.20–6.90 Hz) and
4
13
cerning the oxygen analogs, a few heterocyclic structures were
to the phosphorus ( J(H,P)=2.40–1.70 Hz). The C NMR spectra
[
36,37]
related with amino substituents on the phosphorus.
These
exhibit characteristic resonances for the carbon atom of the
compounds were synthesized from 1,3,2-benzodiazaphosphor-
CS group around d=230 ppm for compounds 1 and 2 and
2
ine compounds (cyclic N P(O)H), which were deprotonated
d=240 ppm for compounds 3 and 4, associated with the cor-
2
1
with sodium hydride and then allowed to react with carbon di-
sulfide, followed by addition of an alkyl halide at room temper-
ature. An interesting phosphoranimide dithioformate ester, as
a red-violet liquid, was obtained by decomposition of a silylat-
ed aminophosphonium dithioformate salt, and presented
responding J(C,P) from 54 to 126 Hz, the highest values corre-
31
spond to compounds 3 and 4. The P NMR values obtained
for these dithioesters show a more pronounced difference in
chemical shift, varying from d=24.82 (1) to 49.60 ppm (2) and
from d=14.65 (3) to 62.45 ppm (4). The IR spectra exhibit
characteristic stretching bands for the thiocarbonyl bonds at
[
38]
good thermal stability.
À1
Our general synthetic route presents a one-pot reaction
from diphenyl or bis(diisopropylamino) phosphine chalcoge-
nides (Scheme 2). Bis(diisopropylamino)phosphine was ob-
n˜ =1097 (1) and 1092 cm (3), whereas the corresponding
values are much lower in the case of the thiophosphinoyl com-
À1
pounds, at n˜ =1071 (2) and 1067 cm (4). These stretching vi-
[
39]
tained as described in the literature.
bration bands are in the range of expected values for C=S
[27,30,34]
Such secondary phosphine oxides or sulfides are quite
bonds involved in a free CS group,
and are strongly de-
2
acidic. Initial deprotonation with n-butyllithium takes place at
pendent on the nature of the chalcogenide. The P=O bonds
0
8C, followed by nucleophilic addition to carbon disulfide. The
also provide strong vibration as expected at n˜ =1190 (1) and
À1
1218 cm (3), whereas the P=S
bands absorb at lower wave
numbers of n˜ =722 (2) and
À1
6
87 cm (4).
These compounds were de-
signed to be used in radical
polymerization, which occurs in
most cases above ambient tem-
perature. A study of their ther-
mal stability, under typical poly-
merization conditions of solvent,
concentration, and temperature,
was necessary prior to more in-
vestigations. We followed the
Scheme 2. Synthesis of phosphinoyl and thiophosphinoylcarbodithioates (P-RAFT).
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31
1
evolution by P NMR { H} spectroscopy, a solution of
0 nm of the agent in deuterated toluene at 608C (see
Table 1. Crystallographic data for compounds 1–4.
2
for example compound 2, Figure S-5 in the Supporting
Information). The results indicate that compounds 1–4
are totally stable at 608C, as no additional signals were
detected over a period of 48 h. Moreover, the pink-red
color of the solution was unchanged, which is a good in-
dication of the stability of the chain end during polymeri-
zation.
1
2
3
4
chemical
formula
C
21
H19OPS
2
C
21
H
19PS
3
C
21
H
37
N
2
OPS
2
21 37 2 3
C H N PS
M
r
382.45
triclinic
398.54
monoclinic
428.62
monoclinic
444.71
orthorhombic
crystal
system
space
group
a [ꢃ]
b [ꢃ]
c [ꢃ]
P1¯
P2
/c
Cc
1 1 1
P2 2 2
1
8.7336(2)
9.8162(2)
12.0111(2)
9.0388(2)
20.230(5)
90
116.982(16)
90
10.8007(12)
31.284(3)
7.6073(9)
90
107.924(4)
90.00
8.9843(1)
9.8307(1)
27.8402(4)
90
90
90
The crystallographic data of compounds 1–4 are sum-
marized in Table 1 and molecular views of all four struc-
tures are shown in Figures 1 and 2. Each of these deriva-
tives presents a different space group, unlike the Cr-RAFT
12.3448(3)
67.926(1)
85.391(1)
80.037(1)
965.83(4)
2
a [8]
b [8]
[
27]
g [8]
and Mo-RAFT agents previously studied,
which were
3
V [ꢃ ]
1957.2(6)
4
2445.7(5)
4
2458.90(5)
4
isostructural in the triclinic P 1¯ space group, showing no
Z
effect of the nature of the coordinating metal. Here, com-
paring compounds 1 and 2, or compounds 3 and 4,
moving from oxygen to sulfur induces a change in the
crystalline system, but does not significantly affect the
geometry. The sums of the angles around the phospho-
rus atoms, ꢀP=319.09 (1), 315.60 (2), 324.27 (3), and
1
calcd
1.315
1.352
1.164
1.201
À3
[gcm
l [ꢃ]
T [K]
]
0.71073
193(2)
0.364
0.71073
193(2)
0.462
0.71073
193(2)
0.296
0.71073
193(2)
0.376
m (MoKa
)
À1
[
mm
]
crystal size 0.42ꢄ0.26ꢄ0.10 0.24ꢄ0.14ꢄ0.12 0.15ꢄ0.15ꢄ0.10 0.40ꢄ0.28ꢄ0.14
3
[
mm ]
315.378 (4), are in the same range and indicate that the
2
GOF on F 1.023
R
1.044
0.0344
1.004
0.0431
1.037
0.0304
pyramidality of the phosphine moiety is not greatly af-
fected by the substituent. The structures are very similar:
the P=O bonds in compounds 1 and 3 and the P=S
bonds in compounds 2 and 4 are almost identical, as are
the C=S bonds of the thiocarbonyl groups.
0.0417
0.1031
(
I>2s(I))
2
wR
0.0800
0.395
0.0722
0.193
0.0761
0.355
(
I>2s(I))
largest dif- 0.586
ference
peak
À3
[
eꢃ
]
]
hole
À0.419
À0.285
À0.230
À0.161
À3
RAFT polymerization with P-RAFT agents
[eꢃ
RAFT polymerizations of St and nBA were realized in tolu-
ene at 608C in the presence of P-RAFT agents 1–4, and
were initiated with azobisisobutyronitrile (AIBN). The reac-
tant concentrations were chosen so that the ratio of
monomer to P-RAFT initial concentrations was 300. The main
conversion–time data and macromolecular characteristics
(
M , ꢀ) are collected in Table 2. For St, it appears that the
n
nature of the substituent around the phosphorus does not
have a significant effect on the overall rate of the polymeri-
zation. Styrene polymerization exhibits the common features
of a controlled RAFT polymerization, regardless of the nature
of the P-RAFT agent. Polymerizations are slower than with the
Figure 1. Molecular structure of a) compound 1 and b) compound 2 with
thermal ellipsoids drawn at the 50% probability level. Hydrogen atoms and
disordered phenyl groups have been omitted for clarity. Selected bond
lengths [ꢃ] and angles [8]: compound 1: P1ÀO1 1.489(1), P1ÀC1 1.802(1),
P1ÀC2 1.800 (2), P1ÀC3 1.848(2), C3ÀS2 1.635(2), C3ÀS3 1.710(2); C1-P1-C2
[
27]
Cr-RAFT and Mo-RAFT agents previously studied.
This is probably related to a more pronounced stability of
the intermediate radicals with P-RAFT agents. The possibility of
a small fraction of dead PSt chains resulting from irreversible
1
07.73(7), C2-P1-C3 104.37(7), C1-P1-C3 106.99(7). Compound 2: P1ÀS1
.947(1), P1ÀC1 1.817(2), P1ÀC2 1.809(2), P1ÀC3 1.869(2), C3ÀS2 1.632(2),
1
[
40]
termination of intermediate radicals
cannot be ruled out,
C3ÀS3 1.718(2); C1-P1-C2 108.40(8), C2-P1-C3 104.97(8), C1-P1-C3 102.23(8).
and could contribute, together with classically terminated
chains due to AIBN initiation; to the presence of a small but
visible shoulder at around twice the molar mass of the main
peak of the SEC chromatograms (Figure 3b). For the P-RAFT
agents 1 and 2, St polymerization (Table 2, Entries 1–8; Fig-
the M evolution profile for the highest reaction times is no-
n
ticeable (Figure 3a).
This slight deviation is attributed to the contribution of
AIBN-derived chains that are no longer negligible during the
second half of the polymerization, when considering the rate
of decomposition of the initiator under the chosen reaction
conditions. When using the P-RAFT agents 3 and 4 for the
ure 3a) showed an increase of M proportional to the mono-
n
mer conversion that matches the values predetermined by the
[
St] -to-[P-RAFT]0 ratio and, therefore, demonstrates the effi-
0
ciency of these P-RAFT agents. A slight downward curvature in
&
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Table 2. RAFT polymerization of St and nBA in toluene with P-RAFT 1-4,
initiated with AIBN at 608C.
[
a]
[b]
[c]
Entry
P-RAFT
M
t [h]
M
nth
M
n
ꢀ
Conv. [%]
1
2
3
4
5
6
7
8
9
1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
4
3
3
3
3
4
4
4
4
St
St
St
St
St
St
St
St
St
St
St
St
St
St
St
St
nBA
nBA
nBA
nBA
nBA
nBA
nBA
nBA
10.0
20.1
48.1
96.1
10.0
20.1
48.0
96.1
10.0
20.0
48.0
93.3
10.1
20.0
48.0
96.2
0.6
1.0
2.0
3.3
0.6
1.0
2.0
3.3
5200
9200
15300
21500
6600
10050
16700
24900
5450
5350
8800
15300
18900
6800
10350
15950
21200
6200
10350
17400
20300
5650
1.06
1.18
1.25
1.27
1.06
1.17
1.22
1.25
1.08
1.12
1.16
1.16
1.06
1.13
1.19
1.15
1.48
1.34
1.25
1.27
1.26
1.19
1.25
1.29
15.2
28.2
47.8
67.7
19.7
30.6
52.2
78.3
17.0
31.0
55.0
75.0
17.6
30.3
55.4
78.2
9.0
29.0
53.0
72.0
23.0
50.7
70.9
87.2
1
0
9550
1
1
16650
22550
5900
1
1
1
1
1
1
1
1
2
2
2
2
2
2
3
4
5
6
7
8
9
0
1
2
3
4
9950
9750
17800
24900
3950
11850
21300
28750
9300
19950
27600
33950
16900
22300
4560
13860
25630
31100
9800
21050
29100
35850
[
a] Mnth =([M]
by size-exclusion chromatography (SEC) in THF based on PSt standards
for PSt. For P(nBA) samples, M was determined by SEC in THF based on
0
/[P-RAFT]
0
)ꢄ(Conv.)ꢄM
w
(M)+M
w
(P-RAFT).
[b] Determined
n
PSt standards by using the Mark–Houwink–Sakurada parameters of PSt
1
and P(nBA). [c] Determined by H NMR spectroscopy.
Figure 3. a) Evolution of number-average molar-mass values and the disper-
sity during St polymerization mediated by the P-RAFT agents 1–4 and
b) overlay of the SEC chromatograms for the St polymerization in the pres-
ence of the P-RAFT agent 2.
Figure 2. Molecular structure of a) compound 3 and b) compound 4 with
thermal ellipsoids drawn at the 50% probability level. Hydrogen atoms have
been omitted for clarity. Selected bond lengths [ꢃ] and angles [8]: com-
pound 3: P1ÀO1 1.475(2), P1ÀN1 1.655(2), P1ÀN2 1.641(2), P1ÀC3 1.868(3),
C3ÀS2 1.634(3), C3ÀS3 1.720(3); N1-P1-N2 111.56(11), N2-P1-C3 109.62(11),
N1-P1-C3 103.09(11). Compound 4: P1ÀS1 1.948 (1), P1ÀN1 1.668(1), P1ÀN2
As expected, polymerizations of nBA (Table 2, Entries 17–24)
showed appreciably reduced reaction times compared with
those for St because of the intrinsic greater reactivity of the ac-
rylate monomers. For both P-RAFT agents 3 and 4, the evolu-
1
.655(1), P1ÀC3 1.883(1), C3ÀS2 1.638(1), C3ÀS3 1.730(1); N1-P1-N2
107.00(6), N2-P1-C3 103.89(6), N1-P1-C3 104.51(6).
tion of M is proportional to the conversion and fits well to the
n
theoretical values.
These results show quantitative consumption of the P-RAFT
agents and a negligible fraction of AIBN-derived chains even
for high nBA conversions. The ꢀ value remains low throughout
the polymerization and increases slightly at high nBA conver-
sion (ꢀ<1.3). For Table 2, Entry 17, the high dispersity value is
explained by the low conversion and the significant contribu-
tion of the oligomers. These features are also characteristic of
a controlled RAFT polymerization. For the studied P-RAFT
agents 1–4, the controlled Mn values and the quite low ꢀ
values observed even at low monomer conversions for both St
and nBA polymerizations suggest that both the chain transfer
to the P-RAFT agent and the interchain transfer are fast relative
to the propagation step. A fast transfer to the P-RAFT agent 3
St polymerization (Table 2, Entries 9–16; Figure 3a), the M con-
n
version profile matches the theory similarly to that of com-
pounds 1 and 2, but lower values of ꢀ (<1.2) were obtained
at the end of the polymerization.
For all the agents, the ꢀ profile, which is quite constant over
the second part of the polymerization, indicates the chemical
stability of the polymer chain end for long reaction times, with
ꢀ
values up to 1.27–1.25 for compounds 1 and 2 and 1.16–
1.15 for compounds 3 and 4. These features are characteristic
of a controlled RAFT polymerization and are illustrated in Fig-
ure 3b, which shows an overlay of the size-exclusion chroma-
tograms of P(St)s (Table 2, Entries 5–8) during a polymerization
mediated by the P-RAFT agent 2.
31
was confirmed by P NMR spectroscopy for both St and nBA
Chem. Eur. J. 2014, 20, 1 – 10
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polymerizations, with a complete conversion of compound 3
before 17% for St and 9% for nBA (see Figure S-7 in the Sup-
porting Information). As expected for a controlled RAFT poly-
main population corresponds to intact dormant chains; this is
a very relevant point, which indicates the high stability of the
polymer chain-end functionality. Indeed, the loss of the thio-
carbonylthio moiety in MALDI-TOF MS analysis of RAFT poly-
mers, which originates under the experimental conditions of
the ionization, is well known in the literature. The chain-end
functionalities of PSt-RAFT cannot usually be characterized by
31
merization, the P NMR spectra showed the presence of the
phosphorylated polymer chain ends.
To further confirm the controlled character of the polymeri-
zations mediated by this new generation of RAFT agents, and
the integrity of the polymer chain ends, a diblock copolymer
of St and nBA was prepared. To do so, a PSt macro-RAFT agent
[41,42]
[43]
MALDI-TOF MS,
especially in the presence of salts,
whereas the integrity of the chain end is better conserved with
[17,43,44]
(PSt-4) was synthesized in the presence of compound 4 in tol-
polyacrylates or polyvinyl esters for example.
Three
uene at 608C and isolated. Characterization indicates a M of
other minor populations can be distinguished, noted (2), (3),
and (4). Series (2) corresponds to a PSt population with unsatu-
rated termination, whereas series (3) is related with PSt chains
initiated with AIBN. Series (1), (2), and (3) are cationized with
sodium. Series (4), which is cationized with a proton, is attri-
buted to PSt chains w terminated with a thiol group. It is
worth mentioning that no side population originating from
coupling between growing chains was observed for this low
molar mass PSt-4 sample obtained at low St conversion
(ꢀ8%).
n
À1
1100 gmol and a ꢀ of 1.13 (Table S-1, Entry 25, in the Sup-
porting Information). Compound PSt-4 was analyzed by
matrix-assisted laser desorption ionization time-of-flight mass
spectrometry (MALDI-TOF MS). As shown in Figure 4 (and Fig-
ure S-6 in the Supporting Information), the spectrum displays
the main population (1), which is in complete agreement with
the expected PSt bearing P-RAFT 4 groups at both ends, with
R as the a end-group and the thiocarbonylthio moiety as the
+
w terminus; m/z=105+104n+339+23 (Na ), where n is the
degree of polymerization. The difference in m/z between the
The resulting PSt-4 was subsequently used as a macro-RAFT
agent for the AIBN-initiated polymerization of nBA in toluene
peaks corresponds to the molar mass of one styrene unit. The
Figure 4. MALDI-TOF mass spectrum of PSt-4 realized with a 4-(4-nitrophenylazo)resorcinol matrix in presence of trifluoroacetic acid (TFA)-Na in THF.
&
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a strong thermal stability in toluene and was found to mediate
efficiently the RAFT polymerization of St and nBA. The St poly-
merization exhibits the common features of a controlled RAFT
polymerization, regardless of the nature of the P-RAFT agent.
However, slower polymerizations potentially attributed to
a small fraction of irreversible termination involving intermedi-
ate radicals were observed in comparison with previously re-
ported organometallic phosphinocarbodithioate RAFT agents.
The nBA polymerization proceeds with an excellent control
over the M values and low dispersity values. The increase of
n
M is proportional to the monomer conversion and matches
n
the predetermined theoretical values, whereas the dispersity
values are quite low (ꢀ<1.3). The high chain-transfer reactivity
of the P-RAFT agents and the fast formation of P-RAFT-capped
31
polymer chains was evidenced by P NMR spectroscopy. To
extend the controlled character of polymerization of this new
generation of RAFT agents, and to confirm the integrity of the
polymer chain-ends, a diblock copolymer of St and nBA was
prepared. To this end, PSt-RAFT was isolated and characterized
by MALDI-TOF mass spectrometry, which revealed the pres-
ence of both end groups of the starting P-RAFT agent. The fol-
lowing growth of the P(nBA) block was realized in a highly
controlled manner. This work is the beginning of a wider study
of phosphorus-based RAFT agents. Continuing the modulation
of the environment at the phosphorus atom will help us to
identify the spectrum of efficiency of these agents, in terms of
monomers. Later, in situ changes in the functionalities at the
phosphorus atom may lead to novel P-based switchable RAFT
agents.
Figure 5. Evolution of number-average molar-mass values and dispersity
values with conversion of a) nBA and b) overlay of the SEC chromatograms
during nBA polymerization mediated by PSt-4.
Experimental Section
General: The syntheses of the P-RAFT agents 1–4 were carried out
by using standard Schlenk and high-vacuum line techniques under
an argon atmosphere. The RAFT polymerizations were performed
in glass tubes that were sealed under vacuum after three freeze–
evacuate–thaw cycles. NMR spectra were recorded by using
at 608C. Figure 5a shows the controlled growth of the P(nBA)
block as indicated by the increase of M with values fitting per-
n
fectly to theoretical ones for block copolymerization. The ꢀ
value remained quite low with a slight increase at high conver-
sion due to the contribution of dead chains from the initiator.
Figure 5b is an overlay of the size-exclusion chromatograms
during nBA polymerization mediated by PSt-4. The results
summarized in Table S-1 of the Supporting Information (En-
tries 26–29) allowed us to conclude that the PSt-4 precursor
acted as an efficient macro-RAFT agent leading to the corre-
sponding diblock copolymers PSt-P(nBA)-4.
a Bruker AVANCE-300 spectrometer for the samples in CDCl . IR
3
spectra were recorded by using a Thermo Fischer Nexus 6700 FTIR
spectrometer in the ATR mode. Melting points were measured
with a sealed capillary by using the Stuart automatic melting point
SMP40 apparatus. Mass spectra were recorded by using a Nermag
R10-10H or Hewlett Packard 5989A mass spectrometer. MALDI-TOF
MS measurements were performed by using a MALDI Micro MX
(Waters). This instrument is equipped with a nitrogen laser (l=
3
37 nm, 4 ns pulse), a delayed extraction, and a reflector. It was op-
erated at an accelerating potential of 12 kV in the reflectron mode.
The matrix used was 4-(4-nitrophenylazo)resorcinol. Number-aver-
age molar mass (M ) values and dispersity values (ꢀ) of the poly-
n
Conclusion
mer samples were determined by size-exclusion chromatography
(SEC). The SEC analysis was conducted by using a Waters 712 WISP
and R410 differential refractometer with a Styragel column (HR4E)
New phosphinoyl and thiophosphinoylcarbodithioates (P-
RAFT) were synthesized in a one-pot reaction from the corre-
sponding phosphinochalcogenides. Their complete characteri-
zation by spectroscopic and spectrometric methods is de-
scribed, including X-ray analyses. The structures obtained are
very similar and the pyramidality of the phosphine moiety
does not appear to be affected by varying the substituent.
This new generation of phosphorylated compounds presents
À1
in tetrahydrofuran (THF) as an eluent at a flow rate of 1.0 mLmin
(358C). The column system was calibrated with narrow PSt stan-
dards, obtained from Polymer Laboratories, ranging from 400 to
5
À1
1
0 gmol . Values of M are reported in PSt equivalents by using
n
the Mark–Houwink–Sakurada parameters of PSt and P(nBA). The St
and nBA conversions were determined gravimetrically or by
1
H NMR spectroscopy.
Chem. Eur. J. 2014, 20, 1 – 10
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Materials: THF, toluene, and carbon disulfide were purified by con-
Compound 3: a-Methylbenzyl-[bis(N,N-diisopropylamino)phosphi-
noyl]carbodithioate (2.33 g, 85%); m.p. 47–468C; P{ H} NMR
[45]
31
1
ventional methods before use. Diphenylphosphinesulfide,
[39]
1
bis(N,N-diisopropylamino)phosphine,
chloro-bis(N,N-diisopropyl-
bis(N,N-diisopropylamino)phosphine
were prepared following literature methods. Diphenyl-
(121.49 MHz, CDCl3, 258C, H PO ): d=14.65 ppm; H NMR
3
4
[39]
3
amino)phosphine,
and
(300.13 MHz, CDCl , 258C, TMS): d=1.13 (d, J(H,H)=6.80 Hz, 24H;
CH ), 1.61 (d, J(H,H)=7.20 Hz, 3H; CH ), 3.35–3.65 (m, 4H; CH),
4.98 (qd, J(H,H)=7.20, J(H,P)=1.70 Hz, 1H; CH), 7.11–7.30 ppm
(m, 5H; C H ); C{ H} NMR (75.47 MHz, CDCl , 258C, TMS): d=
20.09 (s, CH ), 23.08 (d, J(C,P)=2.80 Hz, NCHCH ), 47.05 (d,
J(C,P)=2.80 Hz, NCHCH ), 48.23 (d, J(C,P)=2.10 Hz, CH), 127.35 (s,
3
[46]
3
oxide
3
3
3
4
phosphine oxide (Aldrich, 97%), diphenylphosphine (Acros, 97%),
n-butyllithium (Aldrich, 1.6m solution in hexane), and (1-bromo-
ethyl)benzene (Aldrich, 97%) were used as received. Styrene (Al-
drich, 99%) was distilled over calcium hydride under reduced pres-
sure and nBA (Acros, 99%) were passed through a column filled
with basic alumina prior to use. AIBN was obtained from Janssen
Chimica and purified by triple recrystallization from methanol.
13
1
6
5
3
3
3
3
2
3
3
C -C H ), 127.89 (s, C -C H ), 128.29 (s, C -C H ), 141.25 (s, Cipso-
m
6
5
p
1
6
5
o
6
5
C H ), 242.60 ppm (d, J(C,P)=126.23 Hz, CS ); IR (neat): n˜ =1218
6
5
2
À1
+
(P=O), 1092 cm (C=S); MS (CI-NH ): m/z: 429 [M+H ]; MS (EI,
3
+
+
7
0 eV): m/z: 323 [M ÀCH(C H )CH ], 247 [M ÀCS CH(C H )CH ],
Synthesis of bis(N,N-diisopropylamino)phosphine sulfide: A solu-
6
5
3
2
6
5
3
+
[38]
105 [M À(iPr N) P(O)CS ].
tion of bis(N,N-diisopropylamino)phosphine (5.99 g, 25.82 mmol)
and S8 (0.91 g, 28.43 mmol) in THF (90 mL) was stirred at room
temperature during 30 min. After removal of the solvent under re-
duced pressure, the product was obtained as a white solid (6.35 g,
2
2
2
Compound 4: a-Methylbenzyl-[bis(N,N-diisopropylamino)thiophos-
phinoyl]carbodithioate
(0.568 g,
P{ H} NMR (121.49 MHz, CDCl
H NMR (300.13 MHz, CDCl , 258C, TMS): d=1.18 (d, J(H,H)=
20%);
m.p.
110–1128C;
31
1
,
3
258C,
H
PO ): d=62.45 ppm;
3
4
3
1
1
1
3
9
3%). P{ H} NMR (121.4 MHz, CDCl , 258C, H PO ): d=31.76 ppm.
3
3
3
4
3
5
6
.90 Hz, 24H; CH ), 1.65 (dd, J(H,H)=7.20, J(H,P)=1.20 Hz, 3H;
3
3
General synthetic procedure for 1–4: The solution of the corre-
sponding phosphine chalcogenide (6.40 mmol) in THF (20 mL) was
treated with a stoichiometric amount of n-butyllithium (4.0 mL,
3
CH ), 3.74 (sept, J(H,H)=6.90 Hz, J(H,P)=2.10 Hz, 4H; CH), 4.80
3
3
4
(qd, J(H,H)=7.20, J(H,P)=2.40 Hz, 1H; CH), 7.09–7.31 ppm (m,
13
1
5
H; C H ); C{ H} NMR (75.47 MHz, CDCl , 258C, TMS): d=20.20 (s,
6 5 3
3 2
1
.6m in hexane) at 08C and the yellow mixture was stirred for
CH ), 23.55 (d, J(C,P)=2.26 Hz, NCHCH ), 48.02 (d, J(C,P)=3.47 Hz,
NCHCH ), 50.96 (d, J(C,P)=2.11 Hz, CH), 127.43 (s, C -C H ),
3
3
6
0 min. Then a large amount (excess) of CS (2 mL, 33 mmol) was
2
3
3
m
6
5
added dropwise at 08C to yield a red solution. The mixture was al-
lowed to warm up to room temperature and stirred for 30 min. (1-
Bromoethyl)benzene (1.75 g, 9.45 mmol) was added, and the dark
red solution was stirred for additional 2 h at 10–158C. After remov-
al of the solvent under reduced pressure, the residual product was
subjected to column chromatography (silica gel, cyclohexane/di-
ethyl ether (1:4 v/v)). All compounds were obtained as oily pink-
red materials. Recrystallization from a dichloromethane/pentane
1
2
6
28.11 (s, C -C H ), 128.26 (s, C -C H ), 141.26 (s, Cipso-C H ),
p 6 5 o 6 5 6 5
1
40.61 ppm (d, J(C,P)=95.10 Hz, CS ); IR (neat): n˜ =1067 (C=S),
2
À1
+
87 cm (P=S); MS (CI-NH ): m/z: 445 [M+H ]; MS (EI, 70 eV):
3
+
+
+
m/z: 339 [M ÀCH(C H )CH ], 263 [M ÀCS CH(C H )CH ], 105 [M
6
5
3
2
6
5
3
À(iPr N) PSCS ].
2
2
2
Crystallographic data collection and structure determination for
1–4: The data were collected at low temperature on a Bruker-AXS
SMART APEX II diffractometer (for compounds 1, 2, and 4) or on
a Bruker-AXS APEX II QUAZAR diffractometer (compound 3)
1
mixture (1:10) led to the crystalline compounds. The H NMR spec-
tra of compounds 1–4 are shown in the Supporting Information
(
Figures S-1 to S-4).
equipped with a 30 W air-cooled microfocus source by using Mo a
K
radiation (l=0.71073 ꢃ). Phi- and omega-scans were used. The
Compound 1:
thioate (0.538 g, 22%); m.p: 122–1248C; P{ H} NMR (121.49 MHz,
a-Methylbenzyl-(diphenylphosphinoyl)carbodi-
31
1
data were integrated with SAINT, and an empirical absorption cor-
[47]
1
rection with SADABS was applied. The structures were solved by
CDCl , 258C, H PO ): d=24.87 ppm; H NMR (300.13 MHz, CDCl ,
3
3
4
3
[
48]
3
5
direct methods (SHELXS-97)
and refined by using the least-
2
5
5
58C, TMS): d=1.74 (dd, J(H,H)=7.20, J(H,P)=0.90 Hz, 3H; CH ),
3
3 4
2
squares method on F . All non-hydrogen atoms were refined with
anisotropic displacement parameters. The hydrogen atoms were
refined isotropically at calculated positions by using a riding
model.
.23 (qd, J(H,H)=7.20, J(H,P)=2.10 Hz, 1H; CH), 7.25–7.37 (m,
H; C H ), 7.41–7.61 (m, 6H; C H ), 7.78–7.91 ppm (m, 4H; C H );
6
5
6
5
6
5
1
3
1
C{ H} NMR (75.47 MHz, CDCl , 258C, TMS): d=20.41 (s, CH ),
3
3
4
9.20 (s, CH), 127.86 (s, C - C H ), 127.99 (s, C -C H ), 128.36
m 6 5 p 6 5
3
CCDC 952380 (1), CCDC-952381 (2), CCDC-952382 (3), and CCDC-
(
d, J(C,P)=12.45 Hz, C -C H ), 128.69 (s, C - C H ), 130.19 (d,
m 6 5 o 6 5
J(C,P)=104.98 Hz, Cipso-C H ), 132.35 (s, C - C H ), 132.50 (d,
J(C,P)=7.32 Hz, C - C H ), 140.12 (s, C -C H ), 234.95 ppm (d,
1
9
52383 (4), contain the supplementary crystallographic data for
6
5
p
6
5
2
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.
o
6
5
ipso
6
5
1
À1
J(C,P)=76.08 Hz, CS2); IR (neat): n˜ =1190 (P=O), 1097 m
+
(
2
C=S); MS (CI-NH ): m/z: 383 [M+H ]; MS (EI, 70 eV): m/z:
3
+
+
+
45 [M ÀSCH(C H )CH ], 201 [M ÀCS CH(C H )CH ], 105 [M
General polymerization procedures: A stock solution that con-
tained the monomers, the P-RAFT agents 1–4, AIBN, and toluene
was prepared in the following concentrations, respectively:
6
5
3
2
6
5
3
ÀPO(C H ) CS ].
6
5 2
2
Compound 2: a-Methylbenzyl-(diphenylthiophosphinoyl)carbodi-
À1
À1
À1
31
1
[St] =6.33 molL , [P-RAFT] =21 mmolL , [AIBN] =7.4 mmolL
;
thioate (0.764 g, 30%); m.p. 112–1148C; P{ H} NMR (121.49 MHz,
0
0
0
À1
À1
1
[nBA] =5.33 molL ,
[P-RAFT] =17.8 mmolL ,
[AIBN] =
0
CDCl , 258C, H PO ): d=49.60 ppm; H NMR (300.13 MHz, CDCl ,
0
0
3
3
4
3
À1
3
5
6.2 mmolL . Aliquots (4 mL) were transferred to four tubes, de-
gassed with three freeze–evacuate–thaw cycles and the tubes
were sealed under vacuum. The sealed tubes were heated at 608C
for the requisite times in an oil bath equipped with a thermostat.
The sealed tubes were removed at given intervals and cooled rap-
idly. An aliquot of the reaction mixture was taken, the excess
amount of monomer and solvent was removed by evaporation at
ambient temperature under vacuum and the residues was ana-
lyzed by using SEC.
2
5
5
58C, TMS): d=1.73 (dd, J(H,H)=7.20, J(H,P)=1.20 Hz, 3H; CH ),
3
3 4
.08 (qd, J(H,H)=6.90, J(H,P)=2.40 Hz, 1H; CH), 7.26–7.36 (m,
H; C H ), 7.39–7.58 (m, 6H; C H ), 7.76–7.91 ppm (m, 4H; C H );
6
5
6
5
6
5
1
3
1
C{ H} NMR (75.47 MHz, CDCl , 258C, TMS): d=20.27 (s, CH ), 51.08
3
3
3
(
s, CH), 127.94 (s, C -C H ), 127.96 (s, C -C H ), 128.27 (d, J(C,P)=
m 6 5 p 6 5
1
1
2.90 Hz, C -C H ), 128.63 (s, C -C H ), 131.27 (d, J(C,P)=87.16 Hz,
m 6 5 o 6 5
2
Cipso-C H ), 132.03 (s, C -C H ), 132.46 (d, J(C,P)=15.54 Hz, C -C H ),
6
5
p
6
5
o
6
5
1
1
40.17 (s, Cipso-C H ), 233.19 ppm (d, J(C,P)=54.57 Hz, CS ); IR
6 5 2
À1
(
neat): n˜ =1071 (C=S), 722 cm (P=S); MS (CI-NH ): m/z: 399
3
+
+
+
[M+H ]; MS (EI, 70 eV): m/z: 293 [M ÀCH(C H )CH ], 217 [M
Synthesis of PSt-4: A solution that contained AIBN, RAFT agent 4,
6
5
3
+
À1
À1
ÀCS CH(C H )CH ], 105 [M ÀPS(C H ) CS ].
St, and toluene ([St] =6.32 molL , [4] =0.062 molL , [AIBN] =
0 0 0
2
6
5
3
6
5 2
2
&
&
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Full Paper
À1
0
.021 molL ) was prepared, transferred to a tube, degassed, and
[16] H. Skaff, T. Emrick, Angew. Chem. Int. Ed. 2004, 43, 5383–5386; Angew.
Chem. 2004, 116, 5497–5500.
the tube was sealed. The solution was heated at 608C for 15 h.
The PSt-4 was isolated by evaporation of the residual monomer
[
17] P.-E. Dufils, G. David, B. Boutevin, G. Woodward, G. Otter, A. Guinau-
deau, S. Maziꢁres, M. Destarac, J. Polym. Sci. Part A 2012, 50, 1997–
2007.
under reduced pressure (737 mg, 7.8% conversion, M =
n
À1
1
100 gmol , ꢀ=1.13 (Table S-1, Entry 25, in the Supporting Infor-
[
18] C. Boyer, V. Bulmus, P. Priyanto, W. Y. Teoh, R. Amal, T. P. Davis, J. Mater.
Chem. 2009, 19, 111–123.
mation).
Synthesis of PSt-b-P(nBA) copolymers: PSt-4 (737 mg) was pre-
pared as described above, nBA (8.57 g), AIBN (36.24 mg), and tolu-
ene (2.6 mL) were transferred to a glass tube and the tube was
sealed and heated at 608C for the requisite times. Volatile material
was removed under reduced pressure to give the PSt-b-P(nBA) co-
polymers (Table S-1, Entries 26–29, in the Supporting Information).
[19] R. Pçtzsch, S. Fleischmann, C. Tock, H. Komber, B. I. Voit, Macromolecules
2011, 44, 3260–3269.
[
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Acknowledgements
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lꢀculaire” GDRI and the Embassy of France in Kiev are grateful-
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·
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·
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Revised: November 12, 2014
Published online on && &&, 0000
Chem. Eur. J. 2014, 20, 1 – 10
www.chemeurj.org
9
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
FULL PAPER
&
Polymerization Agents
S. Maziꢁres,* I. Kulai, R. Geagea,
S. Ladeira, M. Destarac*
&& – &&
Phosphinoyl and
Phosphorus RAFTing: Novel phosphi-
noyl and thiophosphinoylcarbodi-
thioates have been synthesized and
were fully characterized, including by X-
ray analysis. They are efficient transfer
agents for the reversible addition–frag-
mentation chain transfer polymerization
of styrene and n-butyl acrylate, and re-
lated block copolymerization (see
figure).
Thiophosphinoylcarbodithioates:
Synthesis, Molecular Structure, and
Application as New Efficient Mediators
for RAFT Polymerization
&
&
Chem. Eur. J. 2014, 20, 1 – 10
www.chemeurj.org
10
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!