Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with secondary phosphine sulfides: Synthesis of adducts

Article abstract of DOI:10.1016/j.jorganchem.2013.07.050

Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with diphenylphosphine sulfide have been carried out. Reaction proceeds under radical initiation (AIBN, 63-68 C, 2.5 h, THF, reactants molar ratio = 1:1) to afford the ant

Full text of DOI:10.1016/j.jorganchem.2013.07.050

Journal of Organometallic Chemistry 745-746 (2013) 126e132
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Mass spectrometry and quantum chemical studies of the reaction of
divinyl telluride with secondary phosphine sulfides: Synthesis of
adducts
Nina K. Gusarova, Nataliya A. Chernysheva, Lyudmila V. Klyba, Vladimir A. Shagun,
*
Svetlana V. Yas’ko, Vladimir I. Smirnov, Boris A. Trofimov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Mass spectrometry and quantum chemical studies of the reaction of divinyl telluride with diphenyl-
phosphine sulfide have been carried out. Reaction proceeds under radical initiation (AIBN, 63e68 ꢀS,
2.5 h, THF, reactants molar ratio ¼ 1:1) to afford the anti-Markovnikov monoadduct 1 and diadduct 2 in
67 and 23% yield, respectively. The former easily decomposes to give vinyldiphenylphosphine sulfide 3
(in 63% yield), ethylene and elemental tellurium, the structure of which represents mainly nano-sized
powder consisting of agglomerates with average size of 350e450 nm. The comparative analysis of
electron ionization mass spectra of compounds 1, 2 and 3 indicates that the presence of tellurium atom in
adducts 1 and 2 reduces stability of their molecular ions and hinders the elimination of sulfur atom.
Under conditions of chemical ionization of phosphine sulfides 1 and 3, the process of their protonation
with CHþ5 followed by the elimination of sulfur atom from [ON]þ ion is dominant. These data are also
confirmed by the results of quantum chemical calculations of the most stable protonated structures of
phosphine sulfides 1 and 3.
Received 24 April 2013
Received in revised form
16 July 2013
Accepted 18 July 2013
Keywords:
Divinyl telluride
Diphenylphosphine sulfide
Adducts
Mass spectra
Quantum chemical calculations
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
2.1:1) react with divinyl telluride to deliver diadducts of anti-
Markovnikov type in good yields [3].
Divinyl telluride, which has become available due to the
development of the method for its synthesis by direct reaction of
acetylene with metal tellurium [1,2], represents a promising
building block for organic and elementoorganic synthesis [2e6].
Divinyl telluride is capable of participating in different types of
reactions due to the presence of several reactive sites in its mole-
cule. For example, divinyl telluride reacts with bromine [5] and
selenium dichloride [4] to afford the corresponding divinyl tellu-
ride bromide and -dichloride [4,5]. Divinyl telluride is oxidized by
hydrogen peroxide to divinyl tellurone [2]. The reaction of divinyl
telluride with organyl halogenides furnishes telluronium salts [2].
Under radical initiation [2], divinyl telluride adds thiols to the
double bonds against the Markovnikov’s rule to give mono- or
diadducts [2].
The present communication reports essentially new data ob-
tained by more detailed investigation of this reaction. The work is
also aimed at mass spectrometry study of mono- and diadducts
formed from divinyl telluride and secondary phosphine sulfides,
since the data related to mass spectra of functional tertiary phos-
phine sulfides are limited in literature, and those of tertiary phos-
phine sulfides containing organyltelluride groups are absent at all.
Quantum chemical calculations of the most stable protonated
structures of these compounds have been performed to addition-
ally explain the mechanism of phosphine sulfides decomposition.
2. Results and discussion
We have found that the heating (63e68 ꢀC, 2.5 h, THF) of divinyl
telluride with diphenylphosphine sulfide (their molar ratio is
w1:1) in the presence of AIBN regioselectively gives a mixture of
mono- and diadducts 1 and 2 in 2.3:1 ratio (1H and 31P NMR)
(Scheme 1).
Recently, we have shown that secondary phosphine sulfides
under certain conditions (AIBN, 63e68 ꢀC, reactants molar ratio
Diadduct 2 was isolated from the reaction mixture in 23% iso-
lated yield. For this, the reaction mixture (after THF distillation) was
diluted with ether and telluride 2 (insoluble in ether) was filtered.
* Corresponding author. Fax: þ7 3952 419346.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.07.050

N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
127
ions is won by the former, i.e. the most part of ionic current be-
longs to phosphorus-containing ions.
AIBN, 63-68 o
THF
C
S
S
Decomposition of molecular ion of phosphine sulfide 1 proceeds
via three competitive directions involving the cleavage of CeP and
CeTe bonds and formation of [M ꢁ C2H3]þ with m/z 375,
[M ꢁ C2H3Te]þ with m/z 245 and [Ph2PS]þ with m/z 217 (Scheme 3).
The most intensive peak is attributed to [Ph2PS]þ ion. Further
decomposition of the formed ions obeys the known regularities
established for phosphine sulfides bearing aromatic substituents [7].
It should be noted that during the fragmentation of compound
1, sulfur atom remains intact both in molecular ion and
main fragment ions. However, it is a common knowledge that
phosphine sulfides are characterized by elimination of sulfur
atom from Mþ [7e10]. Nevertheless, in the case of phosphine
sulfide 1, elimination of sulfur atom or sulfur-containing particles
is observed only at deeper stages of the primary ions
decomposition.
To estimate the effect of tellurium atom on character of mo-
lecular ion decomposition of adduct 1, we have analyzed the frag-
mentation data obtained for diphenylvinylphosphine sulfide 3 and
its oxygen analog 4. Unlike tellurium-containing phosphine sulfide
1, in the mass spectrum of phosphine sulfide 3, the peak of mo-
lecular ion with m/z 244 possesses the highest intensity. Interest-
ingly, the character of fragmentation of the latter coincides with
decomposition of oxygen analog 4 [9]. Besides, the mass spectrum
of phosphine sulfide 3 expectedly contains peaks of [M ꢁ S]þ. with
m/z 212 (9%) and [M ꢁ HS]þ with m/z 211(10%) ions, which are
typical for nonfunctional triorganylphosphine sulfides [7e10],
while in the mass spectrum of phosphine oxide 4, peaks of
[M ꢁ P]þ and [M ꢁ HP]þ ions are absent.
P
+
+
P
Te
H
Te
1
S
S
+
P
P
Te
2
Scheme 1. The reaction of divinyl telluride with diphenylphosphine sulfide.
Monoadduct 1 (67% yield) remained in ether solution. It turned out
that unlike diadduct 2, which was stable on long storage under
usual conditions, monoadduct 1 easily decomposed at room tem-
perature to afford diphenylvinylphosphine sulfide 3 (63% yield) and
metal tellurium. Besides, ethylene was also released (it was iden-
tified by qualitative reaction with potassium permanganate)
(Scheme 2).
It should be noted that the morphology of metal tellurium,
released during the decomposition of monoadduct 1 (Scheme 2),
significantly differs from that of usual brand tellurium. For example,
according to scanning electron microscopy (SEM), the synthesized
metal tellurium represents mainly nano-sized powder consisting of
agglomerates with average size of 350e450 nm (Fig. 1a), whereas
brand tellurium comprises microcrystals of irregular form having
rather big sizes (4e36 mm) (Fig. 1b).
The structure of tertiary phosphine sulfides 1e3 synthesized has
been confirmed by the data NMR and MS spectroscopy. One should
emphasize that GSeMS study of these compounds may be of spe-
cial interest since the results obtained are nontrivial and can
essentially complement the known data related to behavior of
tertiary phosphine sulfides in the conditions of electron and
chemical ionization.
The analysis of electron ionization (EI) and chemical ionization
positive ion (CI) mass spectra of functional tellurium-containing
phosphine sulfides 1, 2 has been carried out in comparison with
the data of similar spectra of vinyldiphenylphosphine sulfide 3 and
its heteroanalogue, vinyldiphenylphosphine oxide 4.
Thus, the comparative analysis of EI mass spectra of compounds
1 and 3 testifies that the presence of tellurium atom in monoadduct
1 reduces stability of its molecular ion and hinders the elimination
of sulfur atom.
Unlike monoadduct 1, under EI diadduct 2 forms unstable mo-
lecular ion, the latter being decomposed at the moment of ioniza-
tion. The mass spectrum of diadduct 2 contains peaks of three
series of ions. The minor series of ions is generated via elimination
of Ph2PH molecule by the molecular ion to afford the ion with m/z
434, which further decomposes to consecutively release radicals
C2H3Te and HS or radical SPh (Scheme 4).
High intensity of the ion with m/z 244 (57%) is likely due to
partial thermal decomposition of diadduct 2 in the input system.
Two main series of ions are owing to two odd-electron frag-
ments with m/z 402 and m/z 218 formed by diadduct 2 molecular
ion (Scheme 5). The fragment with m/z 402 contains Te atom, and
character of its fragmentation (main ions with m/z 375, 245, 217,
183, 185, 139) completely corresponds to the decomposition of
monoadduct 1 described above in detail (Scheme 3).
The fragmentation pattern of other ion with m/z 218 (main ions
with m/z 185, 183, 152, 140, 109, 108, 107, 63) coincides with frag-
mentation of the initial diphenylphosphine sulfide (Scheme 6).
The study of CI mass spectrum has shown that diphenyl[2-
(vinyltellanyl)ethyl]phosphine sulfide 1 is easily protonated in a gas
phase, and the cluster of peaks of the protonated molecular ion has
the maximum intensity [ON]þ (ITIC ¼ 30%).
The EI mass spectrum of phosphine sulfide 1 shows a charac-
teristic cluster of isotopic peaks of molecular ion with m/z 402 (for
130Tf), the intensity of which is 5% from total ionic current.
The competition between the processes related to charge
localization on phosphorus-containing or tellurium-containing
In the CI mass spectrum of monoadduct 1, peaks of two series of
ions are present. This indicates that ionization of tellurium-
containing phosphine sulfide 1 proceeds via two different routes.
A minor series of ions is caused by the CeP and CeTe bonds
cleavage and is similar to those ions which are observed during EI
(ions with m/z 245, m/z 217, Scheme 3). Generation of these ions can
take place both at decomposition of the protonated molecular ion
and as a result of ionization according to the mechanism of anion
elimination (Scheme 7).
Scheme 2. Decomposition of diphenyl[2-(vinyltellanyl)ethyl]phosphine sulfide 1.

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N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
Fig. 1. SEM image of tellurium: a e prepared according to Scheme 2; b e brand one.
Thus, the protonation process usually prevails in the chemical
ionization of compounds 1, 3, 4 with CHþ5 . For decomposition of
phosphine sulfide 1, the elimination of sulfur atom from [ON]þ ion
(Scheme 8) is typical, whereas during electron ionization, on the
contrary, sulfur-containing ions make the major contribution to
total ionic current (Scheme 3).
To study the chemical ionization-initiated decomposition of
phosphine sulfides 1, 3 and phosphine oxide 4 in the course of their
interaction with SOþ5 cation, we have employed quantum chemical
calculations of structural reorganization of different protonated
forms of compounds 1, 3 and 4.
The calculations have been performed by (DFT) B3LYP method
[11e13] using the SDD (compound 1) and 6-31G (d, p) (compounds
3 and 4) basis sets and GAUSSIAN 98 package program [14]. The
most sterically preferable proton stabilization sites in phosphine
sulfide 1 turn out to be unshared pairs of S and Te heteroatoms.
Protonation of these sites under topologically favorable conditions
proceeds almost without barrier and does not lead to isomeric
reorganization of the compound. The structure 1(SHD) protonated
at thione center is thermodynamically most stable. The relative
stability of 1(SHD) structure is by 8.1 kcal/mol higher than that of
1(TeHD). The direct attack by a proton of phosphine sulfide 1
phosphorus atom is hindered to its spatial isolation. However,
under chemical ionization, the protonation of phosphorus atom is
quite probable. The calculation have shown that this process is
associated with overcoming high activation barrier that leads to
isomeric reorganization of the molecule. The reorganization is
accompanied by the elimination of sulfur atom from a near-to-
sphere environment of the central atom and its subsequent stabi-
lization due to the interaction with tellurium (Scheme 11).
The elimination of sulfur occurs via the transition state (TS1)
(Fig. 2) with overcoming the barrier of 24.8 kcal/mol. Thermody-
namic stability of 1(RHD) structure (Fig. 2) is slightly lower than
Scheme 3. The fragmentation pattern for the diphenyl[2-(vinyltellanyl)ethyl]phos-
phine sulfide 1 under electron ionization.
Second series of ions indicate the main direction of the
decomposition and is associated with elimination of sulfur atom
from [ON]þ ion and the formation of the protonated molecular ion
of diphenyl[2-(vinyltellanyl)ethyl]phosphine with m/z 371 (21%)
(for 130Te, Scheme 8).
In CI mass spectra of phosphine sulfide 3 and phosphine oxide 4
the peaks of the protonated molecular ions are predominant.
Decomposition of [ON]þ ions for phosphine sulfide 3 is due to
the elimination of sulfur atom (ion m/z 213) and benzene molecule
(ion m/z 167, Scheme 9).
In CI mass spectrum of phosphine oxide 4 only one fragmental
ion caused by elimination of a molecule of benzene (ion m/z 151,
Scheme 10) is observed.
It should also be noted the CI ionization of all the compounds
studied 1, 3, 4 involves the processes of electrophilic addition giv-
ing rise to [N þ C2H5]þ and [N þ C3H5]þ ions.
Scheme 4. The minor pathway fragmentation for the molecular ion of diadduct 2 under EI.

N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
129
similar barrier of compound 3 that is due to higher strength of the
S]P bond as compared to the S]S bond. Thermodynamic sta-
bility of 4(PHD) is by 16.5 kcal/mol higher than that of 4(OHD
)
structure. Next in stability protonated structures of compounds 3
and 4 are formed via the interaction of proton with aromatic
fragments of the compounds giving rise to bimolecular systems (A)
and (C). The relative stability of these states are by 20.4 and
30.6 kcal/mol higher than those 3(SHD) and 4(PHD) structures.
Thus, the calculations have shown that the chemical ionization
of monoadduct 1 most likely involves the elimination of vinyl-
telluranyl fragment and sulfur atom, while chemical ionization of
vinyldiphenylphosphine sulfide 3 leads to elimination of sulfur
atom and the benzene molecule. Chemical ionization of vinyl-
diphenylphosphine oxide 4 should result in the elimination of
benzene molecule only. These conclusions are in good agreement
with experimental data, the CI mass spectra of compounds 1, 3 and
4, (Schemes 7e10).
Scheme 5. The major fragmentation pattern for the molecular ion of diadduct 2 under
EI.
that of 1(TfHD) form (2.0 kcal/mol). Optimum molecular structures
of the initial compound 1, its protonated forms [1(SHD), 1(TeHD),
1(ROD)] and transition state (TS1) are given in Fig. 2.
The most probable protonation sites in phosphine sulfide 3 and
phosphine oxide 4 are S and O heteroatoms, respectively (molec-
ular structures 3(SOþ) and 4(POþ) are given in Fig. 3). Similar to
phosphine sulfide 1, protonation of phosphorus atom in compound
3 leads to the elimination of S heteroatom from near-to-sphere
environment of the phosphorus atom. As a result, the protonated
structure 3(ROD) is stabilized in the state, where sulfur atom,
coordinating with the vinyl fragment, forms the thiirane cycle
(Scheme 12, Fig. 3). The activation barrier of this process is by
2.5 llam/npm: lower than that of TS1 equaling 22.3 kcal/mol.
Thermodynamic stability of 3(PHD) is by 12.6 kcal/mol lower than
that of 3(SHD).
At the same time, the protonated structure of compound 4,
4(PHD) is not capable of initiating the formation of the oxirane
cycle but leads to sigmatropic rearrangement of the vinyl fragment
and generation of formation RePeSO]SO2 chain (Scheme 12,
Fig. 3). The rearrangement barrier is 11.8 kcal/mol higher than the
3. Conclusion
In conclusion, divinyl telluride reacts with diphenylphosphine
sulfide in the presence of AIBN (reactants molar ratio ¼ 1:1) to
predominantly afford the anti-Markovnikov monoadduct 1 as well
as diadduct 2. The adduct 1 easily decomposes at room tempera-
ture to afford vinyldiphenylphosphine sulfide, i.e. divinyl telluride
is vinylating agent of secondary phosphine sulfides. The data of
electron ionization mass spectra of compounds 1, 2 and 3 indicates
that the presence of tellurium atom in adducts 1 and 2 reduces
stability of their molecular ions and hinders the elimination of
sulfur atom. At the same time, in chemical ionization of phosphine
sulfides 1 and 3, the process of their protonation with CHþ5 fol-
lowed by the elimination of sulfur atom from [ON]þ ion is
dominant. The results of quantum chemical calculations of the
most stable protonated structures of phosphine sulfides 1 and 3
are discussed.
Scheme 6. The fragmentation pattern for the molecular ion of diphenylphosphine sulfide under EI.
Scheme 7. Main fragment ions in the SI mass spectrum of diphenyl[2-(vinyltellanyl)ethyl]phosphine sulfide 1 formed according to the mechanism of anion elimination.

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N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
Scheme 8. The fragmentation pattern for the protonated molecular ion of adduct 1 under chemical ionization.
4. Experimental
4.3. Reagents
4.1. General conditions
Starting divinyl telluride was prepared as described in the
literature [1]. Diphenylphosphine sulfide was synthesized from
equimolar amounts of diphenylphosphine and elemental sulfur in
ethanol at room temperature.
All steps of the experiment were carried out in argon atmo-
sphere. Tetrahydrofuran was purified by distillation from sodium/
benzophenone ketyl.
4.4. The reaction of divinyl telluride with diphenylphosphine sulfide
4.2. Instruments
A solution of divinyl telluride (0.078 g, 0.43 mmol) and AIBN
(0.008 g, 5% from reactant weight) in THF (2 mL) was blown with
argon and heated up to 60 ꢀS on stirring with a magnetic stirrer.
Then a solution of diphenylphosphine sulfide (0.09 g, 0.41 mmol) in
THF (1 mL) was added drop-wise. The reaction mixture was stirred
with a magnetic stirrer for 2.5 h at 63e68 ꢀS. The solvent was
removed under reduced pressure to give 0.13 g orange copper-like
product. The latter, according to the 31R NMR data, consisted of
monoadduct 1 (dp ¼ 44.96 ppm) and diadduct 2 (dp ¼ 45.00 ppm),
the signals intensity being 70% and 30%, respectively. The ether
Fourier transform IR spectra were run on a Bruker Vertex 70
instrument. The 1H and 31P NMR spectra were recorded on a Bruker
AV-400 spectrometer (400.13 and 161.98 MHz, respectively) and
referenced to H3PO4 (31P NMR) as external standard. Melting points
(uncorrected) were measured on a Kofler micro hot stage appa-
ratus. The microanalyses were performed on a Flash EA 1112 Series
elemental analyzer. Microstructure and chemical composition of
tellurium samples were studied using TN3000 scanning micro-
scope (Hitachi) equipped with Quantax 50 analyzer.
EI mass spectra were run on GCeMS QP-5050A Shimadzu mass
spectrometer at 70 eV with the source temperature fixed at 200 ꢀC.
The compounds were introduced through a direct insertion probe
heated at the minimum temperature necessary to obtain repro-
ducible ion abundances. The chemical ionization mass spectra were
obtained by using Agilent 5975C MSD instrument equipped with
chemical ionization source. The source temperature was approxi-
mately 150 ꢀC. Samples were introduced into the source by means
of the gas chromatograph GC-6890N (Agilent Technologies)
O
+
CH5
+
H
M
+ CH4
Ph2P
4
m/z 151 (12%)
+
C6H6
through capillary column HP-5MS (30 m ꢂ 0.25 mm ꢂ 0.25
mm),
Scheme 10. The fragmentation pattern for the protonated molecular ion 4 under
chemical ionization.
the helium being the gas-carrier. Positive CI mass spectra were
recorded with CH4 as reagent gas.
S
+
CH5
H
M+
+
CH4
m/z 167 (4%)
H+
Ph2P
3
+
C6H6
+ S
+
Ph2P
m/z 213 (9%)
Scheme 9. The fragmentation pattern for the protonated molecular ion
3
under
Scheme 11. Structural reorganization of phosphine sulfide 1 due to the protonation of
chemical ionization.
phosphorus atom.

N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
131
Fig. 2. Main structural characteristics of compound 1, its protonated forms and transition state (TS1) (B3LYP/SDD). The distances are given in angstroms.
Fig. 3. Molecular structures and main geometry characteristics of thermodynamically most stable protonated forms of compounds 3 and 4 (3LYP/6-31G(d,p). The distances are
given in angstroms.

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N.K. Gusarova et al. / Journal of Organometallic Chemistry 745-746 (2013) 126e132
Scheme 12. Structural reorganization of phosphine sulfide 3 and phosphine oxide 4 due to the protonation of phosphorus atom.
(5 mL) was added to a mixture of mono- 1 and diadduct 2. The
residue precipitated. The ether was decanted and the procedure
was repeated trice. The precipitate obtained was dried to afford
0.03 g (23%) of diadduct 2. The ether extracts were combined,
concentrated under reduced pressure and the residue was dried in
vacuo to give orange viscous product A (0.085 g), containing black
inclusions (elemental tellurium). According to 31R NMR spectrum
(C6D6), product A is a mixture of monoadduct 1 (dp ¼ 44.96 ppm)
and diphenylvinylphosphine sulfide 3 (dp ¼ 36.52 ppm).
Acknowledgment
This work was supported by the Russian Foundation for Basic
ꢀ
Research (grant N . 11-03-00286) and the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-1550.2012.3).
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J. Cioslowski, J.V. Ortiz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham,
C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill,
B.G. Johnson, W. Chen, M.W. Wong, J.L. Andres, M. Head-Gordon,
E.S. Replogle, J.A. Pople, Gaussian 98, Revision A.9, Gaussian, Inc., Pittsburgh,
PA, 1998.
(400.13 MHz, C6D6):
(m 8H, p-HPh). 31P NMR (161.98 MHz, C6D6):
cmꢁ1): 3052 (]CH of phenyl rings), 2931, 2902 (CH), 1477 (C]C of
phenyl rings), 1434, 1394 ( CH2), 1310, 1248, 1180, 1154, 1139, 1102,
1069, 1026, 998, 928, 841, 762 ( CH of phenyl rings), sh 752 (PeC),
744, 715, 706, 699 ( CH of phenyl rings), 675, 623, 611, 603 (P]S),
589 (SeTf), 499, 486, 456, 430. Anal. Calcd. for S28H28P2S2Te
(618.2): C, 54.62; H, 4.47; P, 10.07; S, 10.52; Te, 20.59. Found: C,
54.40; H, 4.57; P, 10.02; S, 10.37; Te, 20.64%.
d
2.80 (m 8H, CH2), 7.07 (m 12H, m,p-HPh), 7.93
d
44.99. IR (KBr,
n,
d
d
d