Synthesis, Characterization, and Reactivity of Metalla-Chalcogenirenium Compounds?

Article abstract of DOI:10.1002/cjoc.202000745

Chalcogenirenium cations, featuring an unsaturated three-membered organic ring, are limited but known to be synthesizable from alkynes with bulky electron-donating groups. Metalla-chalcogenirenium compounds have been synthesized as stable compounds throug

Full text of DOI:10.1002/cjoc.202000745

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Accepted Article
Title: Synthesis, Characterization, and Reactivity of Metalla-chalcogenirenium
Compounds
Authors: Ming Luo, Yapeng Cai, Xinlei Lin, Lipeng Long, Hong Zhang,* and Haiping
Xia*
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Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Synthesis, Characterization, and Reactivity of
Metalla-chalcogenirenium Compounds
Ming Luo, #,a Yapeng Cai, #, b Xinlei Lin,b Lipeng Long,b Hong Zhang,*,b and Haiping Xia*,a,b
a Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Sci-
ence and Technology, Shenzhen 518055, People’s Republic of China.
b College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People’s Republic of China.
Dedicated to the 10th anniversary of Southern University of Science and Technology
Keywords
Metalla-chalcogenirenium |DFT calculations | Metallacycles | P-block cations | Aromaticity
Main observation and conclusion
Chalcogenirenium cations, featuring an unsaturated three-membered organic ring, are limited but known to be synthesizable from
alkynes with bulky electron-donating groups. Metalla-chalcogenirenium compounds have been synthesized as stable compounds
through the reactions of a cyclic metal-carbyne complex−metallapentalyne with PhSCl, PhSeCl or PhTeCl. As a result of the high strain
in the three-membered metallacycles, the metalla-chalcogenirenium cations react readily with the base or chloride ions. These reac-
tions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds. The intrinsic stabilization effect of aroma-
ticity is further elucidated by DFT calculations.
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Supporting Information
*E-mail: zh@xmu.edu.cn; E-mail: xiahp@sustech.edu.cn
#These authors contributed equally to this work.
Chin. J. Chem. 2021, 39, XXX－XXX
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First author et al.
Report
demonstrated good compatibility and efficiency of this reaction in
which different chalcogen reagents can readily participate to af-
ford the corresponding products (2a-2c). The compounds (2a-2c)
were characterized by nuclear magnetic resonance (NMR) spectra
and elemental analysis (EA). For 2a, the three proton signals at
14.41, 10.16, and 9.57 ppm are assigned to H1, H3, and H5, re-
spectively. With the aid of DEPT-135 and 1H-13C HSQC (100.6 MHz,
CD2Cl2), the 13C NMR signals of 2a were assigned to 235.9 ppm
(C1), 218.6 ppm (C7), 192.5 ppm (C4), 167.4 ppm (C5), 163.5 ppm
(C3), 154.4 ppm (C6), and 141.8 ppm (C2). The signals of C7 and
C1 are downfield from that of C4, suggesting the carbene charac-
ters of these two atoms. The 31P NMR spectrum of OsPPh3 dis-
plays two doublets at δ = –8.22 ppm (d, JP-P = 270.5 Hz) and –18.37
ppm (d, JP-P = 270.5 Hz) because the phenyl group is bent out of
the plane of the 3-membered ring. Analogous phenomena were
observed in the NMR data of complexes 2b and 2c. The 13C NMR
signals for C7 in the newly formed three-membered ring are
shifted significantly downfield due to the influence of different
chalcogen cations (218.6 ppm (2a), 233.4 ppm (2b), and 239.9
ppm (2c)). The 77Se NMR spectrum of 2b and 125Te NMR spectrum
of 2c show resonances at 39.8 ppm (JP-Se = 39.5 Hz) and 1238.3
ppm (br), respectively, which are more upfield than the reported
selenirenium (between –79 and –185 ppm) and tellurirenium ions
(between –380 and –426 ppm). [7] This might be attributed to the
interaction between selenium or tellurium atom with osmium.
Background and Originality Content
Reactive p-block cations with weakly coordinating anions have
been the focus of considerable research investigating their
structure, bonding, and reactivity, especially in view of the utility
of such species in catalysis.[1,2] In the case of Group VIA, most of
the isolable examples, such as [S8]·+,[3] [Nap(SPh)(SePh)]+,[4]
Ph5Te+,[5] and [MesTe(EPh3)]+ (E = P, As, Sb)[6] depend on
delocalization and other electronic or steric effects for their
relatively high ionization potentials and electronegativities. Thus,
the obviously heavier cation species, especially selenirenium and
tellurirenium ions, i.e. unsaturated three-membered cationic
chalcogen (Ch)-containing ring, have been unstable transient
intermediates. In 2008, Poleschner et al. treated disubstituted
+
-
-
alkynes with (MeSe)3 SbCl6 or PhTe+SbF6 to give the first
selenirenium and tellurirenium cations (Scheme 1a).[7] In a similar
fashion, they recently reported oxidative generation of [RS]+ and
the synthesis of thiirenium salts.[8,9] To date, however, synthetic
studies
of
such
chalcogenirenium
cations
or
metalla-chalcogenirenium cations are scarce, perhaps due to the
lack of suitable precursors and efficient synthetic routes. The only
known examples of three-membered metalla-chalcogenirenium
cations are metallathiirenium species, which were prepared by
the reaction of thiocarbyne with acid or addition of [RS]+ to
carbyne complexes.[10] However, metallaselenirenium and
metallatellurirenium ions have never been reported.
Scheme
2
Synthesis of osma-chalcogenirenium cations
).
(2) by
The unsaturated three-membered cationic Ch-containing ring
have been assumed as important intermediates in addition
reactions of PhChCl with the osmapentalyne (
1
[11]
reactions of chalcogenium-containing electrophiles to alkynes
Ph
Ch
or carbon-heteroatom coupling reactions of metal-carbynes[12]
.
2BF4
PPh3
1
Ph
eq.
ChCl
NaBF
Isolation of these reactive chalcogenirenium cations would help
better understand the mechanism of electrophilic additions of
organochalcogen cation ([RCh]+) to alkynes or metal-carbynes,
however, this seems very challenging. Our interest in new building
blocks for metallacycles[13] prompted us to examine the previously
rare family of metalla-chalcogenirenium cations. Inspired by
metalla-aromatic chemistry,[14,15] we speculated that the
ambiphilic nature of the metal-carbyne units in metallapentalynes
should be susceptible to [RCh]+, and could be utilized as excellent
building blocks that, with an electrophilic addition reaction, could
produce the desired metalla-chalcogenirenium cations.
Cl
7
[Os]
[Os]
2
4
R
R
PPh3
6
2
RT, 1 h
4
5
3
1
2
=
=
=
:
:
:
=
2a
2b
2c
Ch
Ch Se
Ch
S
92%
90%
95%
,
OsCl(PPh3 2
[Os]
)
=
R
,
,
COOMe
Te
Adding ether to a concentrated solution of 2a or 2b in
dichloromethane allowed for the formation of single crystals
suitable for an X-ray diffraction study. As shown in Figure 1,
complexes 2a and 2b are tricyclic systems with
a
metalla-chalcogenirenium ring fused to metallapentalene
rings. The mean deviation from the least-squares plane
Scheme 1 Synthesis of chalcogenirenium or metalla-chalcogenirenium
cations by electrophilic addition of organochalcogen cations [RCh]+ to
alkynes or cyclic metal-carbynes.
through the nine atoms is 0.0803 Å (Os1, C1–C7, S1) for 2a
,
indicating that the tricyclic metallacycle units are essentially
planar. The C–C bond distances of the osmapentalene rings
are in the range of 1.370–1.412 Å (2a), which are comparable
to those of reported metallapentalenes with electron
delocalized metallacyles.[13] In the case of 2a, the C7–S1
(1.709 Å) and Os1–S1 bonds (2.631 Å) are slightly longer than
those of osmathiirene (1.643 Å and 2.563 Å),[16] while the
Os1–C7 bond length (1.957 Å) is shorter (2.000 Å in
osmathiirene).[16] On the other hand, the C7–S1 (1.709 Å) in
Ions
reactions of
(a) Cyclic chalcogenirenium
by
alkynes
R
+
Ch +
Ch
[R
=
]
Bulky
strategy
groups
protecting
Ch
Se, Te
S,
=
Bulky
groups
metalla-chalcogenirenium Ions
reactions of
metal-carbynes
cyclic
(b) Cyclic
by
R
+
Ch
Ch +
]
[M]
[R
S,
2a is much shorter than the corresponding bonds in
[M]
Aromaticity-driven strategy
=
Ch
Se, Te
-
thiireniums
([tBu2C2SMe]+BF4 :
1.820
Å;[8b]
work
this
[tBu2C2SMe]+CH-B11Cl11 : 1.832 Å). [7] The angle subtended at
the chalcogen atom of 2a (48.1°) is obviously larger than
those in the reported chalcogenirenium ions (37.6°–41.3°). [7-9]
Although the systematic disorder of 2b in the solid state does
not permit a detailed discussion of bond lengths and angles,
the connectivity of metalla-selenirenium is unambiguously
confirmed. As a supplement to metal-carbyne chemistry,[17] the
-
=Transition metal
[M]
fragments
Results and Discussion
We reacted the osmapentalyne compound (1)[16] with PhChCl
(Ch = S, Se, Te) at room temperature (RT). As indicated by NMR
spectra, stirring a mixture of 1, PhChCl and two equivalents of
NaBF4 in dichloromethane for 1 h resulted in almost quantitative
conversion of 1 to the complexes 2 (Scheme 2). The results
reactions of cyclic metal-carbynes
1 with PhChCl (Ch = Se, Te)
expand the understanding of electrophilicity of metal-carbynes
and led to the first examples of three-membered
metalla-selenirenium cation and metalla-tellurirenium cation.
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Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
Figure 1 X-ray molecular structures for the cations of 2a (a) and 2b (b) with
50% probability ellipsoids. Hydrogen atoms in the phenyl moieties are
omitted for clarity. Selected bond lengths [Å] and angles [deg] for 2a:
Os(1)−C(1) 2.016(3), Os(1)−C(4) 2.125(3), Os(1)−C(7) 1.957(3), Os(1)−S(1)
2.6306(9), C(7)−S(1) 1.709(3); Os(1)−C(1)−C(2) 123.5(2), C(7)−Os(1)−S(1)
40.50(9), C(7)−S(1)−Os(1) 48.06(12), S(1)−C(7)−Os(1) 91.44(15).
Compounds
2 can be stored in the solid state at ambient
temperature under air for over a week without noticeable
decomposition. The solid samples of 2a and 2b can even
survive 3 hours at 60 °C in air. Its aromaticity may account for
the
stability
of
the
three-membered
metalla-chalcogenirenium cation (
2
). Nucleus-independent
Figure 2 Aromaticity evaluation. (a) NICS(1)zz values (in ppm) for the model
2' calculated at the B3LYP/6-311++G(d,p) level. [Os]' = OsCl(PH3)2. (b) ACID
isosurface of model 2a' from all π-MOs contribution. Current density
vectors are plotted onto the ACID isosurface of 0.030 to indicate diatropic
ring currents. The magnetic field vector is orthogonal with respect to the
ring plane and points upward (clockwise currents are diatropic). (c) The
isodesmic reactions resulting from breaking the Ch−Os bonds in different
types of three membered fused rings. The energies, including the
zero-point energy corrections, are given in kcalꢀmol−1.
chemical shifts (NICS) were calculated,[18] based on the
unsubstituted model compounds 2' in which PH3 groups were
used to replace the PPh3 ligands in 2. In general, negative
NICS values indicate aromaticity, and positive NICS values
indicate anti-aromaticity. As shown in Figure 2a, the
calculated NICS(1)zz value for the three fused metallacycles
(rings A, B, and C) of 2' are all negative, revealing the
aromatic nature of these rings. Together with the bending of
the phenyl substituents out of the planes of the
three-membered rings, we think the aromaticity of the
three-membered metalla-chalcogenirenium cations
closely related to the reported metallacyclopropenes with
σ-aromaticity.[19] The aromaticity of
was further confirmed
It is noteworthy that the fused metallapentalene rings in
2 are
2
play a crucial role in the remarkable stabilization of the
metalla-chalcogenirenium skeleton. The stability of the
three-membered metalla-chalcogenirenium cation has also
2
2
been studied by means of isodesmic reactions,[22] in which
the types and numbers of chemical bonds in the reactants
are the same as those in the products (Figure 2c). As
expected, a positive value of the computed reaction energies
is shown for model compound 2'. The difference between
the reaction energies in two equations can be attributed to
the aromaticity of the three membered ring in 2'. The loss of
the support of fused metallapentalene is the origin of the
endothermicity of the two equations in Figure 2c. This raises
an intriguing possibility of the future synthesis of
chalcogenirenium cations through aromaticity-driven
strategy, which would provide promising expansion of this
reactive p-block cation family.
by the anisotropy of the induced current density (ACID)
analysis.[20] The electron delocalization within the
metallacycles can be visualized by the clockwise current
density vectors plotted on the ACID isosurface employing all
π-molecular orbitals of model 2a' (Figure 2b). Further
calculations show that the natural bond orbital (NBO) charge
at the chalcogen atom increases from S (0.510) through Se
(0.737) to Te (1.023). These values are comparable to those
found for typical chalcogenirenium[7] and chalcogeniranium
cations[21]
.
The rich chemistry of unsaturated three-membered
rings[23] promoted us to explore the reactivity of
metalla-chalcogenirenium cations. The reaction at 80 °C in
dichloroethane of 2a or 2b with Bu4NCl provided complexes
3a or 3b, respectively (Scheme 3). Complex 3b was
determined to be a substitution product of 2b, in which one
of the PPh3 ligands at the osmium center was replaced by a Cl
ligand (Figure 3a). Nevertheless, complex 2c rapidly
underwent a decomposition reaction with Bu4NCl reverting
to
reactions of 2a
agreement with the more electropositive chalcogen atoms
supported by the calculated NBO charges. Moreover,
proved to be extremely sensitive to base. Thanks to the
positive charge in these aromatic systems, the addition of
1
in a stoichiometric fashion. The different outcomes of
/2b or 2c with chloride ion are in good
2
5
equivalents of pyridine to 2a or 2b at room temperature
quantitatively converted each compound into a new cyclic
Chin. J. Chem. 2021, 39, XXX－XXX
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First author et al.
Report
=
=
=
COOMe, Ch
S,
h R
OsCl(PP
,
)
Te
Se,
carbyne species (4a or 4b) (Scheme 4) with the elimination of
HBF4. In the presence of excess pyridine, 2c was converted to
[Os]
Ph
3 2
Ph
Ch
1
, similar to the reaction with chloride ion. Single crystal X-ray
Ch
[Os]
structural analysis reveals to result from the uptake of one
4
[Os]
PPh3
H atom of the metallapentalene ring by base, producing a
metallapentalyne ring (Figure 3b). The distance between Os
and Se in 4b (3.380 Å) is much greater than those in 2b (2.752
Å) and 3b (2.705 Å), which indicates a ring-opening of the
three-membered metalla-chalcogenirenium ring. The 77Se
NMR spectroscopy of 4b (666.7 ppm) is more downfield than
that of 3b (461.7 ppm) due to the absence of any interactions
between selenium and osmium, however, both 77Se reso-
nances are more downfield than that of 2b (39.8 ppm).
Similar reactions of chalcogenirenium ring with nucleophiles
have been demonstated in literature.[24] Interestingly, rapid
recovery of the three-membered metalla-chalcogenirenium
ring can be achieved by the addition of an acid, such as
R
PPh3
R
2B
2A
Ph
R
Ph
R
Ch
Ch
[Os]
[Os]
PPh3
PPh3
2C
2D
Figure 4 Resonance structures for the cationic moiety of 2.
Conclusions
In summary, the synthesis, reactivity studies and DFT calcula-
tions of the metalla-chalcogenirenium species have been achieved.
Similar to typical chalcogenirenium or chalcogeniranium cations,
chalcogen atoms in these metalla-chalcogenirenium compounds
are Lewis acidic and susceptible to interaction with Lewis bases.
Notably, computational studies suggest the aromaticity of the
three-membered metalla-chalcogenirenium rings and indicate that
the fused metallapentalene rings play a substantial role in the
stabilization of three-membered p-block cation frameworks, which
are otherwise difficult to prepare.
excess tetrafluoroboric acid, to the solution of 4a or 4b
.
Scheme 3 Reactions of osma-chalcogenirenium cations 2.
Ph
Ch
BF4
[Os]''
1
Bu NCl
4
eq.
80 o 4 h
PPh3
R
C,
3
=
PPh3
70%
85%
OsCl2
[Os]''
=
:
3a
Ch
S,
=
Ch
Se
S,
=
:
3b
Ch Se,
Experimental
Ph
Ph
Ch
BF4
PPh3
All reactions were carried out under an inert atmosphere (N2)
using standard Schlenk techniques. Solvents were distilled from
calcium hydride (dichloromethane and dichloroethane) or
sodium/benzophenone (hexane and diethyl ether) under N2.
The osmapentalyne 1 was synthesized as reported by the
published procedure[16] and benzenetellurenyl chloride[25] was
prepared in situ by the reaction of Ph2Te2 and SO2Cl2 and used
immediately. Other reagents were used as purchased from
commercial sources without further purification. NMR data were
obtained on a Bruker AVII-400 (1H 400.1 MHz; 31P 162.0 MHz; 13C
5
eq.
pyridine
RT, 5 min
Ch
[Os]
2BF4
PPh3
[Os]
R
R
1.2
HBF Et2O
eq.
RT, 5 min
4
4
2
=
=
:
95%
4a
4b
Ch
Ch Se,
S,
=
PPh
OsCl(
COOMe
:
95%
[Os]
)
3 2
=
R
=
Te
Ch
1
or
Bu
4NCl
pyridine
RT, 5 min
100.6 MHz) spectrometer at room temperature. In H and 13C
1
NMR, tetramethylsilane is used as the reference, and 31P NMR
chemical shifts are relative to 85% H3PO4. One-dimensional and
two-dimensional NMR are abbreviated as distortionless
enhancement by polarization transfer (DEPT), heteronuclear
single quantum coherence (HSQC) and heteronuclear multiple
bond correlation (HMBC). The coupling constants are expressed
in Hertz (Hz). The abbreviations for multiplicities are singlet (s),
doublet (d) and broad (br). EAs were collected on a Vario EL III
elemental analyzer.
Synthesis and characterization of complex 2a: The mixture of
complex 1 (286 mg, 0.24 mmol), NaBF4 (53 mg, 0.48 mmol), and
PhSCl (35 mg, 0.24 mmol) in dichloromethane (10 mL) were
stirred for one hour at room temperature. The reddish−yellow
solution was filtered and evaporated under vacuum to a small
volume. The precipitate was produced by adding diethyl ether and
collected by filtration and dried under vacuum to give 2a (295 mg,
Figure 3 X-ray molecular structures for the cations of 3b (a) and 4b (b) with
50% probability ellipsoids. Hydrogen atoms in the phenyl moieties are
omitted for clarity. Selected bond distances (Å) and angles (deg): for 3b:
Os(1)−C(1) 2.017(6), Os(1)−C(4) 2.112(6), Os(1)−C(7) 1.936(6), Os(1)−Se(1)
2.7055(6), C(7)−Se(1) 1.875(6); Os(1)−C(1)−C(2) 122.7(4), C(7)−Os(1)−Se(1)
43.86(18), C(7)−Se(1)−Os(1) 45.68(17), Se(1)−C(7)−Os(1) 90.5(3). For 4b:
Os(1)−C(1) 1.841(5), Os(1)−C(4) 2.074(5), Os(1)−C(7) 2.082(5), C(7)−Se(1)
1.888(5); Os(1)−C(1)−C(2) 130.1(4), C(7)−Os(1)−Se(1) 116.7(3).
92%) as an orange solid. H NMR plus H-13C HSQC (400.1 MHz,
CD2Cl2): δ = 14.43 (br, 1H, H1), 10.41 (s, 1H, H3), 9.71 (s, 1H, H5),
3.66 (s, 3H, COOCH3), 7.96–6.94 ppm (m, 50H, Ph). 31P NMR (162.0
MHz, CD2Cl2): δ = 13.61 (s, CPPh3), –8.22 (d, JP-P = 270.5 Hz,
OsPPh3), –18.37 ppm (d, JP-P = 270.5 Hz, OsPPh3). 13C NMR plus
DEPT-135 and 1H-13C HSQC (100.6 MHz, CD2Cl2): δ = 235.9 (br, C1),
218.6 (br, C7), 192.5 (d, JP-C = 20.1 Hz, C4), 167.4 (s, C5), 163.5 (br,
1
1
Above experimental and computational results indicate
that the metalla-chalcogenirenium cation
(2
)
can be
represented by the resonance structures 2A
-2D (Figure 4).
1
C3), 158.4 (s, COOCH3, confirmed by H-13C HMBC), 154.4 (s, C6),
141.8 (d, JP-C = 81.6 Hz, C2), 52.6 (s, COOCH3), 137.3–127.6 ppm (m,
Ph). Anal. Calcd (%) for C69H56B2ClF8O2OsP3S: C 57.49, H 3.92;
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Running title
Chin. J. Chem.
Found: C 57.67, H 4.28.
COOCH3), 7.80–7.22 ppm (m, 35H, Ph). 31P NMR (162.0 MHz,
CD2Cl2): δ = 13.28 (s, CPPh3), –17.44 ppm (s, OsPPh3). 13C NMR
plus DEPT-135 and 1H-13C HSQC (100.6 MHz, CD2Cl2): δ = 237.1 (br,
C1), 232.2 (d, JP-C = 8.63 Hz, C7), 191.4 (d, JP-C = 20.3 Hz, C4), 162.6
Synthesis and characterization of complex 2b: The mixture of
complex 1 (286 mg, 0.24 mmol), NaBF4 (53 mg, 0.48 mmol), and
PhSeCl (46 mg, 0.24 mmol) in dichloromethane (10 mL) were
stirred for one hour at room temperature. The reddish−yellow
solution was filtered and evaporated under vacuum to a small
volume. The orange precipitate was produced by adding diethyl
ether and collected by filtration and dried under vacuum to give
1
(s, C5), 160.0 (s, COOCH3, confirmed by H-13C HMBC), 157.2 (d,
JP-C = 19.6 Hz, C3), 156.2 (s, C6), 141.0 (d, JP-C = 79.5 Hz, C2), 53.9 (s,
COOCH3), 136.1–128.6 ppm (m, Ph). 77Se NMR (76.3 MHz, (CD2Cl2))
δ = 461.7 (s). Anal. Calcd (%) for C51H41BCl2F4O2OsP2Se: C 52.14, H
3.52; Found: C 52.38, H 3.95.
2b (298 mg, 90%) as an orange solid. H NMR plus H-13C HSQC
1
1
(400.1 MHz, CD2Cl2): δ = 14.51 (br, 1H, H1), 10.22 (s, 1H, H3), 9.68
Synthesis and characterization of complex 4a: Pyridine (16 μL,
1.00 mmol) was added to dichloromethane solution complex 2a
(268 mg, 0.20 mmol). The mixture was stirred for 5 min at room
temperature. The reddish solution was evaporated under vacuum
to a small volume. The red precipitate was produced by adding
diethyl ether and collected by filtration, washed with diethyl ether
and dried under vacuum to give 4a (247 mg, 95%) as a red solid.
1H NMR plus 1H-13C HSQC (400.1 MHz, CD2Cl2): δ = 8.65 (s, 1H, H5),
7.44 (m, included in Phenyl groups, 1H, H3), 2.92 (s, 3H, COOCH3),
7.77–6.29 ppm (m, 50H, Ph). 31P NMR (162.0 MHz, CD2Cl2): δ =
5.01 (t, JP-P = 5.0 Hz, CPPh3), –0.77 ppm (d, JP-P = 3.9 Hz, OsPPh3).
(s, 1H, H5), 3.75 (s, 3H, COOCH3), 8.00–7.02 ppm (m, 50H, Ph). 31
NMR (162.0 MHz, CDCl3): δ = 13.26 (s, CPPh3), –10.05 (d, JP-P
P
=
213.8 Hz, OsPPh3), –21.09 ppm (d, JP-P = 213.8 Hz, OsPPh3). 13C
NMR plus DEPT-135 and H-13C HSQC (100.6 MHz, CDCl3): δ =
1
236.6 (br, C1), 233.4 (br, C7), 191.2 (d, JP-C = 20.1 Hz, C4), 168.6 (s,
C5), 165.0 (br, C3), 159.1 (s, COOCH3, confirmed by 1H-13C HMBC),
156.8 (s, C6), 142.3 (d, JP-C = 79.2 Hz, C2), 53.2 (s, COOCH3), 136.8–
127.6 ppm (m, Ph). 77Se NMR (76.3 MHz, (CD2Cl2)) δ = 39.8 (d, JPSe
= 39.5 Hz). Anal. Calcd (%) for C69H56B2ClF8O2OsP3Se: C 55.68, H
3.79; Found: C 55.93, H 4.12.
1
Synthesis and characterization of complex 2c: To a stirred
solution of bisphenyl ditelluride (49.1 mg, 0.12 mmol) in CH2Cl2
(5.0 mL) was added SO2Cl2 (18.9 mg, 0.14 mmol) at r.t. to prepare
benzenetellurenyl chloride in situ. After the color of the reaction
mixture turned orange to dark red (ca. 1 h), the solution was
added into complex 1 (286 mg, 0.24 mmol) and NaBF4 (53 mg,
0.48 mmol) in dichloromethane (10 mL) and the mixture was
stirred for one hour at room temperature. The solution was
filtered and evaporated under vacuum dried under vacuum to
13C NMR plus DEPT-135 and H-13C HSQC (100.6 MHz, CD2Cl2): δ =
322.4 (br, C1), 231.7 (t, JP-C = 8.17 Hz, C7), 176.8 (d, JP-C = 22.9 Hz,
1
C4), 165.5 (s, COOCH3, confirmed by H-13C HMBC), 156.7 (s, C5),
152.9 (s, C6), 151.3 (d, JP-C = 14.9 Hz, C3), 120.5 (d, JP-C = 91.1 Hz,
C2), 51.5 (s, COOCH3), 135.5–127.9 ppm (m, Ph). Anal. Calcd (%)
for C69H55BClF4O2OsP3S: C 61.22, H 4.10; Found: C 60.77, H 4.07.
Synthesis and characterization of complex 4b: Pyridine (16 μL,
1.00 mmol) was added to dichloromethane solution complex 2b
(277 mg, 0.20 mmol) (268 mg, 0.20 mmol). The mixture was
stirred for 5 min at room temperature to give a reddish solution.
The solution was evaporated under vacuum to a small volume.
1
1
give 2c (326 mg, 95%) as an orange solid. H NMR plus H-13C
HSQC (400.1 MHz, CD2Cl2): δ = 14.51 (br, 1H, H1), 9.83 (s, 1H, H3),
9.55 (s, 1H, H5), 3.73 (s, 3H, COOCH3), 8.43–6.91 ppm (m, 50H, Ph). The red precipitate was produced by adding diethyl ether and
31P NMR (162.0 MHz, CD2Cl2): δ = 13.57 (s, CPPh3), –14.00 (d, JP-P
=
collected by filtration, washed with diethyl ether and dried under
260.8 Hz, OsPPh3), –25.59 ppm (d, JP-P = 260.8 Hz, OsPPh3). 13C
vacuum to give 4b (256 mg, 95%) as a red solid. H NMR plus
1
1
NMR plus DEPT-135 and H-13C HSQC (100.6 MHz, CD2Cl2): δ =
1H-13C HSQC (400.1 MHz, CD2Cl2): δ = 8.62 (s, 1H, H5), 7.33 (m,
included in Phenyl groups, 1H, H3), 2.97 (s, 3H, COOCH3), 7.79–
6.54 ppm (m, 50H, Ph). 31P NMR (162.0 MHz, CD2Cl2): δ = 5.06 (t,
JP-P = 5.4 Hz, CPPh3), –2.53 ppm (d, JP-P = 4.8 Hz, OsPPh3). 13C NMR
plus DEPT-135 and 1H-13C HSQC (100.6 MHz, CD2Cl2): δ = 322.1 (br,
C1), 236.4 (t, JP-C = 9.1 Hz, C7), 179.1 (d, JP-C = 22.8 Hz, C4), 165.7 (s,
246.9 (br, C1), 239.9 (br, C7), 189.0 (d, JP-C = 20.1 Hz, C4), 168.0 (s,
C5), 162.1 (d, JP-C = 16.9 Hz, C3), 159.8 (s, COOCH3, confirmed by
1H-13C HMBC), 151.7 (s, C6), 114.6 (d, JP-C = 79.2 Hz, C2), 53.9 (s,
COOCH3), 138.3–116.5 ppm (m, Ph). 125Te NMR (126.2 MHz,
(CD2Cl2))
δ
=
1238.3 (br).
Anal. Calcd (%) for
1
C69H56B2ClF8O2OsP3Te: C 53.92, H 3.67; Found: C 53.67 H 3.53.
Synthesis and characterization of complex 3a: The complex
2a (268 mg, 0.20 mmol) and Bu4NCl (55.6 mg, 0.20 mmol) in
COOCH3, confirmed by H-13C HMBC), 157.0 (s, C6), 154.5 (s, C5),
152.1 (d, JP-C = 16.3 Hz, C3), 120.2 (d, JP-C = 89.6 Hz, C2), 51.6 (s,
COOCH3), 135.6–127.9 ppm (m, Ph). 77Se NMR (76.3 MHz, (CD2Cl2))
δ = 666.7 (s). Anal. Calcd (%) for C69H55BClF4O2OsP3Se: C 59.17, H
3.96; Found: C 59.12, H 4.08.
Conversion of complex 4a to complex 2a: Complex 4a (13.1
mg, 0.01 mmol) reacted with HBF4·Et2O (6 μL, 0.012 mmol) in
CD2Cl2 (0.5 mL) for 5 min at room temperature in an NMR tube,
o
dichloroethane was stirred for 4 hours at 80 C. The solution was
filtered and evaporated under vacuum to a small volume. The
brown precipitate was produced by adding diethyl ether and
collected by filtration, washed with diethyl ether and dried under
1
vacuum to give 3a (150 mg, 70%) as a brown solid. H NMR plus
1H-13C HSQC (400.1 MHz, CDCl3): δ = 14.18 (br, 1H, H1), 9.88 (s, 1H, complex 4a transformed into complex 2a in 100% NMR yield.
H3), 9.77 (s, 1H, H5), 3.82 (s, 3H, COOCH3), 8.26–6.98 ppm (m, 50H,
Conversion of complex 4b to complex 2b: Complex 4b (13.5
mg, 0.01 mmol) reacted with HBF4·Et2O (6 ul, 0.012 mmol) in
CD2Cl2 (0.5 mL) for 5 min at room temperature in an NMR tube,
complex 4b transformed into complex 2b in 100% NMR yield.
Conversion of complex 2c to complex 1: To solution of com-
plex 2c (286 mg, 0.20 mmol) in dichloromethane (0.2 mL), a solu-
tion of pyridine (16 μL, 1.00 mmol) was added. The reaction mix-
ture was stirred for 5 min at room temperature The solution was
evaporated under vacuum to a volume of approximately 2 mL,
then diethyl ether (20 mL) was added to the solution. The red
precipitate was collected by filtration, washed with diethyl ether
(2 × 5 mL) and dried under vacuum to give 1 (230 mg, 96%).
Crystallographic Analysis. Crystals suitable for x-ray diffraction
were grown from dichloromethane solution layered with hexane.
Single crystal X-ray diffraction data were collected on an Oxford
Gemini S Ultra CCD Area Detector with graphite-monochromated
MoKa radiation (λ = 0.71073 Å). All of the data were corrected for
absorption effects by using the multiscan technique. With
Ph).31P NMR (162.0 MHz, CDCl3): δ = 15.28 (s, CPPh3), –14.52 (s,
1
OsPPh3) 13C NMR plus DEPT-135 and H-13C HSQC (100.6 MHz,
CDCl3): δ = 236.7 (br, C1), 217.2 (d, JP-C = 9.5 Hz C7), 193.3 (d, JP-C
=
20.8 Hz, C4), 165.6 (s, C5), 163.7 (d, JP-C = 18.8 Hz, C3), 159.9 (s,
1
COOCH3, confirmed by H-13C HMBC), 155.4 (s, C6), 142.3 (d, JP-C
=
82.8 Hz, C2), 53.0 (s, COOCH3), 135.7–126.4 ppm (m, Ph). Anal.
Calcd (%) for C51H41BCl2F4O2OsP2S: C 54.31, H 3.66; Found: C 54.54,
H 4.04.
Synthesis and characterization of complex 3b: The complex
2b (277 mg, 0.20 mmol) and Bu4NCl (55.6 mg, 0.20 mmol) in di-
chloroethane was stirred for 4 hours at 80 oC to give solution. The
solution was filtered and evaporated under vacuum to a small
volume. The brown precipitate was produced by adding diethyl
ether and collected by filtration, washed with diethyl ether and
dried under vacuum to give 3b (191 mg, 85%) as a brown solid. 1H
1
NMR plus H-13C HSQC (400.1 MHz, CD2Cl2): δ = 14.09 (d, JP-H
=
12.3 Hz, 1H, H1), 9.72 (s, 1H, H5), 9.51 (s,1H, H3), 3.88 (s, 3H,
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de

First author et al.
Report
Olex2,[26] the structure was solved using the ShelXT[27] structure
solution program and refined with the ShelXL[28] refinement
package using least-squares minimisation. All of the non-hydrogen
atoms were refined anisotropically unless otherwise stated. The
hydrogen atoms were placed at their idealized positions and
assumed the riding model unless otherwise stated. All
non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were placed at idealized positions and assumed the riding
model. X-ray crystal structures have been deposited in the
Cambridge Crystallographic Database under the deposition
numbers CCDC 1916574 (2a), CCDC 1983245 (2b), CCDC 1916575
(3b), and CCDC 1916576 (4b). These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Computational details. All the calculations were performed
with the Gaussian 09 software package.[29] The structures 2a-2c
were optimized by M06L/6-31G*, and then the natural bond or-
bital (NBO) analysis were performed at the M06L/6-311G** level.
The structures 2a’, 2b’, 2c’ were optimized by B3LYP/6-31G*, and
then the NICS and ACID calculations were performed at the
B3LYP/6-311++G** level.[30] The structures of 1-Ch, 2-Ch, 3-Ch,
4-Ch, 5-Ch were optimized by wB97XD/6-31+G**. The effective
core potentials (ECPs) of Hay and Wadt with a double-ζ valence
basis set (SDD for M06L, and LanL2DZ for B3LYP) were used to
describe Os, P, Cl, S, Se, and Te atom, whereas the standard
6-31G*, 6-311G** or 6-311++G** basis set was used for C, O, and
H.[31] Polarization functions were added for Os (ζ(f) = 0.886), P(ζ(d)
= 0.340), Cl (ζ(d) = 0.514), S (ζ(d) = 0.421), Se (ζ(d) = 0.0.338) and
Te (ζ(d) = 0.237).[32]
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Acknowledgement
We gratefully acknowledge the National Natural Science
Foundation of China (No. U1705254, 21871225, and 21931002),
Shenzhen Science and Technology Innovation Committee (No.
JCYJ20200109140812302), and the Fundamental Research Funds
for the Central Universities (20720190042). We thank Dr Liu Leo
Liu for constructive criticism of the manuscript.
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Chin. J. Chem. 2021, 39, XXX－XXX
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Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
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Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
Entry for the Table of Contents
Synthesis, Characterization, and Reactivity of Metalla-chalcogenirenium Compounds
Ming Luo, Yapeng Cai, Xinlei Lin, Lipeng Long, Hong Zhang,* and Haiping Xia*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
R
+
Ch
Ch +
[M]
[R
S,
]
[M]
=
Te
Ch
Se,
metal
=Transition
[M]
fragments
Aromaticity-driven strategy for the first examples of three-membered metalla-selenirenium cations and metalla-tellurirenium cations.
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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