A Monomeric Tricobalt(II)-Substituted Dawson-Type Polyoxometalate Decorated by a Metal Carbonyl Group: [P2W15O56Co3(H2O)3(OH)3Mn(CO)3]8-

Article abstract of DOI:10.1021/acs.inorgchem.7b01231

A monomeric tricobalt(II)-substituted phosphotungstate polyanion, [H₉P₂W₁₅O₆₂Co₃]^9-, is stabilized by the attachement of an organometallic group, {Mn(CO)₃}, for the first time. The resulting polyoxometalate-supported [Mn(CO)₃]⁺ complex (1) can be used as an efficient catalyst in the cycloaddition of CO₂ with epoxides under mild reaction conditions with pyrrolidinium bromide as a cocatalyst. Besides, magnetic measurements show that the compound exhibits weaker ferromagnetic interactions at low temperature.

Full text of DOI:10.1021/acs.inorgchem.7b01231

Communication
pubs.acs.org/IC
A Monomeric Tricobalt(II)-Substituted Dawson-Type
Polyoxometalate Decorated by a Metal Carbonyl Group:
8
−
[
P W O Co (H O) (OH) Mn(CO) ]
2 15 56 3 2 3 3 3
Jiage Jia, Yanjun Niu, Panpan Zhang, Dongdi Zhang, Pengtao Ma, Chao Zhang, Jingyang Niu,*
and Jingping Wang*
Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and
Chemical Engineering, Henan University, Kaifeng 475004, Henan, China
*
S Supporting Information
synthesis of monomeric Dawson-type cobalt-substituted POMs
ABSTRACT: A monomeric tricobalt(II)-substituted
is still challenging.
9
−
+
phosphotungstate polyanion, [H P W O Co ] , is
9
2
15 62
3
The [Mn(CO) ] fragment is generally attached to a triangle
3
stabilized by the attachement of an organometallic group,
Mn(CO) }, for the first time. The resulting polyox-
of three contiguous bridging O atoms of a metal−oxo cluster,
6
{
3
forming the kinetically stable d low-spin octahedral 18-electron
+
+
15,16
ometalate-supported [Mn(CO) ] complex (1) can be
3
moieties fac-[(OC) ML ] (L = ligand).
POMs, as a kind o+f
3
3
used as an efficient catalyst in the cycloaddition of CO2
with epoxides under mild reaction conditions with
pyrrolidinium bromide as a cocatalyst. Besides, magnetic
measurements show that the compound exhibits weaker
ferromagnetic interactions at low temperature.
multidentate ligand, can coordinate with the [M(CO)3]
fragment, forming a new branch of POMs, namely, POM-
supported metal carbonyl derivatives (PMCDs). Recently, some
PMCDs have already been catalogued in the literature.
Nevertheless, reports about Dawson-type PMCDs remain
1
7−21
relatively rare (Table S1).
Herein, a metal carbonyl compound was involved in the
ransition-metal-substituted polyoxometalates (TMSPs)
reaction system of TMSPs, which has become an intriguing
+
T
possess intriguing structure diversity and special properties
result. A POM-supported [Mn(CO) ] complex containing the
3
1
applicable to diverse fields such as materials science, magnet-
mixed-metal cubane [Na(H O) ](NH ) [P W O Co -
2
5
4
7
2
15 56
3
2
,3
4,5
6
ism, and catalysis, which have been focused on recently.
(H O) (OH) Mn(CO) ]·19H O (1) has been successfully
2 3 3 3 2
1
2−
The trivacant Dawson fragment [(α-P W O )] (P W ), an
synthesized by a conventional aqueous solution method, which
is the first example of a monomeric tricobalt(II)-substituted
Dawson-type PMCD. Orange crystals of 1 were prepared in the
2
15 56
2
15
important precursor, has been utilized to make some neotype
7
TMSPs. However, the d-electron-containing metal centers will
12−
simple one-pot reaction of [α-P W O ]
with Co(OAc)2·
seriously affect the structures of TMSPs. Generally, high-valent
2
15 56
V
V
V
IV
4H O and Mn(CO) Br in a slightly acidic (pH 6.0) solution. It is
metals (V , Nb , Ta , and Sn ) produce the trisubstituted
2 5
n−
III
worth noting that the category of the cation is important for the
formation of suitable diffraction-quality crystals. The exper-
imental XRD pattern of sample 1 is basically consistent with the
simulated XRD pattern, which comes from the data of single-
crystal X-ray diffraction (XRD), indicating the phase purity of the
product (Figure S1).
parent species [M P W O ] , while low-valent metals (Fe ,
3
2
II
15 62
II
II
Mn , Ni , and Co ) give rise to the dimeric sandwich-type
species, which are presumably related to the size of the transition
metals, the overall charge of the polyoxometalates (POMs), and
8
other thermodynamic factors. It is worth noting that
preservation of the monomeric P W skeleton has come true
2
15
Single-crystal XRD analysis indicates that 1 crystallizes in the
monoclinic I2/a space group. The detailed crystallographic data
and structure refinement parameters are listed in Table S2.
Complex 1 contains the discrete cluster anion
in spite of using the higher d-electron-containing transition metal
in recent years.
1
1−
In that context, [(FeX) Fe(OH )(P W O )] (X = Cl/
2
2
2
15 59
OH) is the first example of a monomeric Dawson structure
P W O Co (H O) (OH) Mn(CO) ] (1a), Na/NH4+
8−
[
2 15 56 3 2 3 3 3
trisubstituted with low-valent transition metals, in the synthesis
mixed cations, and lattice water molecules. This new polyanion
a can be described as grafting the carbonyl metal group
8
of which a high ionic strength (4 M NaCl) is necessary, while the
1
monomeric Mn-substituted Dawson POM [Mn O (Ac) (α-
{Mn(CO) } onto the tricobalt-substituted POM framework
4
3
3
3
8−
P W O )] is prepared by a fragment of the prototypal
Mn } complex in a CH COOH/H O solution. The decorated
cubane-type [Mn Mn O ] is the key fragment to immobilize
{P W Co O } (Figure 1), which is similar to that of the
2
15 56
2
15
3
62
9
9−
{
previously reported Dawson-type [P W Nb O ] polyoxoan-
ion-supported Re(CO)
(CO)
{Co
1
2
3
IV
2
2 15 3 62
III
+
complex, [P W Nb O Re-
2 15 3 62
W15Co O62} subclass is constructed of a
3
4
3
8−
17
the P W framework. By contrast, the reports on monomeric Ni-
3
] . The {P
} cap embedded in the defect site of the [α-P W O ]
2 15 56
2 3
2
15
9
−14
12−
substituted Dawson POMs are relatively more,
but most
3
O
6
complexes were made under hydrothermal conditions, where
organic ligands play a tunable role for the transition-metal Ni
Received: May 18, 2017
9
−12
cations further capping the P W fragment.
However, the
2
15
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b01231
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
The magnetic behavior of {MnCo O }-containing metal−oxo
3
4
cluster 1 is displayed in Figure 2 as a plot of the product χ T
M
Figure 1. Ball-and-stick and polyhedral representations of polyanion 1a
[
side view (a and b) and top view (c and d)], polyhedral representations
of the cubane {MnCo O } motif (e), and coordination configurations of
3
4
Co (f) and Mn (g). Color code: P, yellow balls; W, azure balls; Co, pink
balls; O, red balls; C, black balls; Mn, green balls; WO octahedra, azure;
6
PO tetrahedra, yellow; CoO octahedra, pink. Water molecules and
4
6
cations are omitted for clarity.
Figure 2. Plots of χ T versus T for 1. Inset: Field dependence of
M
magnetization of 1 at different temperatures.
ligand through six Co−O−W bridged linkages [Co−O, 2.041−
2.064 Å; W−O, 1.743−1.777 Å] and one Co−O−P bond [Co−
O, 2.186−2.240 Å; P−O, 1.544 Å], forming a P W -like
2
18
+
saturated Well−Dawson structure. Then the [Mn(CO) ]
fragment is bonded to a triangle of three contiguous surface O
versus T measured between 1.8 and 300 K in a magnetic field of
3
1000 Oe. The χ
T value at room temperature (300 K) of 9.74
M
−1
atoms of the Co O “crown” in {P W O Co } via three Mn−
emu K mol is much higher than the expected value of 5.63 emu
3
6
2
15 62
3
K mol− for three spin-only Co ions (S = /
1
II
3
and g = 2), which is
2
O−Co bonds. The Co O “crown” is aggregated together by
3
6
three edge-sharing CoO octahedra. The terminal O atom on
associated with the strong orbital contribution of the high-spin
6
2+
24
each of the CoO octahedra is from a coordinated water
octahedral Co . The χ
T versus T curve exhibits a continuous
M
6
molecule. The Mn atom of the {Mn(CO) } fragment affords a
decrease smoothly from 300 K to a minimum of 7.57 emu K
3
−1
distorted six-coordinated octahedral fac configuration defined by
mol at 18 K. Below 18 K, the χ T value increases rapidly to
M
−1
three O atoms from the {P W Co O } subunit and three C
reach a maximum of 7.96 emu K mol at about 5 K and then falls
2
15
3
62
sharply to 7.59 emu K mol− at 1.8 K. The decrease of χ
1
T from
M
atoms from CO (Figure 1g). The {Mn(CO) } unit and Co O
3
3
6
“crown” are connected by three bridged O atoms, notably,
room temperature is due to the characteristic spin−orbit
II
forming a mixed-metal cubane motif, {MnCo O } (Figure 1e).
coupling of the single Co ions, while the sharp upturn of χ
at the low temperature is indicative of the ferromagnetic Co···Co
interactions within the trinuclear spin cluster. Finally, the χ
M
T
3
4
The {MnCo O } cubane is similar to that of the {MnM O }
3
4
3
4
subunit of the {H M O (Mn(CO) ) } (M = Mo/W) polyanion
T
M
2
8
30
2,23
3 2
2
reported by our group.
kinetically stable d low-spin octahedral 18-electron moieties fac-
(OC) ML ] (M = Mn/Re), containing metal tricarbonyl units
The special structure is related to the
value decreases below 5 K, which is related to magnetic
anisotropy. Besides, the field dependences of magnetization for
1 at low temperatures were studied. The result shows that the
6
+
[
3 3
bonded to a trigonal adjacent O atoms on the surface of POMs. It
magnetization increases abruptly to 3.38 μ
kOe, it increases in a relatively linear manner and finally reaches
4.03 μ at 70 kOe, which is still not saturated (Figure 2, inset).
B
at 25 kOe. Above 25
is worth mentioning that, like the capping WO in the Ni-
6
containing Dawson-type analogue [Ni (OH) (H O) P W -
B
3
3
2
3
2
16
9
−
14
O ] , reported by Hill’s group in 2016, the Mn(CO)3
The increase of magnetization is in accordance with the presence
of ferromagnetic interactions, while the lack of saturation is
further indicative of magnetic anisotropy. What is more, the M
versus H/T curves at different temperatures show that the three
lines do not overlap, which further supports the above
5
9
fragment also plays a role of the stabilizing the Dawson-like
P W Co O } unit, which is the key factor of the constitution
{
2
15
3
62
of monomeric low-valent transition-metal-substituted POMs
1
2−
with the well-known [P W O ] ligand.
2
15 56
+
Besides, two neighboring 1a were linked by two [Na(H O) ]
conclusion. The experimental magnetization of 4.03 μ
B
at 70
2
5
bridges to form a dimeric structure (Figure S5b). The Na ion is
coordinated by five O atoms from water molecules and one O
kOe suggests a g factor of 2.6 and is in line with three high-spin
II
1
II
Co ions with an effective spin of /
for each Co center. This
2
atom from the WO (W11) octahedron at the equator of one
result corresponds to an average g factor of 2.4, which obtained
6
T)max of 7.96 emu K mol− at 5 K,
1
polyanion and one O atom from the WO (W8) octahedron of
from the experimental (χ
further manifesting the presence of magnetic anisotropy of the
M
6
the other polyanion. Two Na and four W atoms are almost in the
same plane, forming a hexagonal geometry (Figure S5c). Bond-
valence-sum (BVS) calculations (Tables S3) reveal that the range
of bond valences for the three terminal O atoms on Co sites as
2
5−27
{Co
motif {MnCo
} cluster.
In short, in the special mixed-metal cubane
3
II
7
O }, Co ions represent d high-spin centers (S =
3
4
3
I
6
/ ), whereas the Mn ion is d low-spin (S = 0); therefore,
unpaired electrons will be on the Co centers. The measure-
ments of magnetic susceptibility prove the presence of
2
II
28
0
.284−0.311 Å, confirming that all of them are diprotonated,
while three μ -O atoms (O57, O58, and O59) linking three
adjacent Co ions are monoprotonated, as indicated by the BVS
calculations (1.186, 1.200, and 1.209 Å).
3
2+
ferromagnetic interaction within the basal Co triangle at low
temperature.
3
B
DOI: 10.1021/acs.inorgchem.7b01231
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
2
9
On the basis of previous reports, the catalytic activity of
substituted POMs [(n-C H ) N] [α-M(H O)SiW O ] (M =
Co , Mn , Ni , Fe , and Cu ; x = 5 and 6) are used to catalyze
7
15 4
x
2
11 39
2+
2+
2+
3+
2+
complex 1 in the cycloaddition of CO was studied (Table 1).
2
the reaction of CO with 1,2-epoxypropane, and the deduced
2
3
4
Table 1. Cycloaddition of CO Catalyzed by Catalyst 1 with
Ionic Liquid 2
mechanism is proposed by Sakakura et al. Herein, we
speculated that the reaction mechanism is analogous to that
supposed by Sakakura et al: First, CO2 is activated via
2
a
−
coordination to the Co center. Simultaneously, Br , dissociated
from pyrrolidinium bromide, attacks the C atom of the epoxide.
Then the O atom of CO attacks the C atom of the activated
2
epoxide ring, followed by a ring-opening reaction step, resulting
in the formation of the nucleophilic alkoxide that eventually
reacts with the electrophilic CO to give the cyclic carbonates.
2
In conclusion, a novel Dawson-type PMCD has been
1
2−
successfully isolated by assembling a [(α-P W O )] building
2
15 56
I
II
block with a cubane-like core, {Mn Co O }. The enhanced
3
4
stability of the tricobalt species is most likely attributed to the
unique coordination environment of the tricarbonyl metal group
+
[
Mn(CO) ] . Compound 1 is the first example of monomeric
3
tricobalt(II)-substituted Dawson-type PMCDs. Furthermore, 1
shows high catalytic activity in the cycloaddition of CO with
2
a
Reaction conditions: catalyst 1 (0.23 mol %), epoxides (5 mmol),
epoxides under mild reaction conditions with pyrrolidinium
bromide as a cocatalyst. Most importantly, the strategy of the
introduction of a metal carbonyl compound into the reaction
system of TMSP chemistry has further shown promising results.
More Dawson-type PMCDs containing other transition metals
will be prepared in the future.
b
ionic liquid 2 (8 mol %, 80 mg). CO was charged into an autoclave.
2
c
Determined by gas chromatography using an internal standard
d
technique; the selectivities were over 99% in all cases. Second run.
e
Third run.
The experimental results show that compound 1 is a high active
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01231.
catalyst for the coupling epoxide and CO to afford the cyclic
■
2
*
S
organic carbonate (COC) in 91% yield after 1.5 h at 70 °C under
1.5 MPa with the ionic liquid pyrrolidinium bromide (2; entry 3).
The conversion of epoxide A (glycidyl phenyl ether) was
evaluated by a combination of complex 1 (0.23 mol %) with ionic
liquid (8 mol %), providing a quantitative yield for the COC
product B (3-phenoxy-1,2-propylene carbonate). Complex 1
itself proved to be unproductive, whereas the ionic liquid alone
gave a 38% yield of B (entries 7 and 1). In order to seek optimal
conditions, three factors were investigated in the reaction: (1)
The formation of COC is strongly affected by the reaction
temperature. Raising the reaction temperature from 65 to 70 °C
resulted in a rapid increase of the yield from 60% to 91% (entry
Synthesis, BVS, XRD, IR, EDX, TGA, UV−vis, CV, and
catalytic properties of 1 and the structures of stacking and
{
Na W } clusters (PDF)
2 4
Accession Codes
CCDC 1542974 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
2
). (2) The reaction time also influences the yield of COC. When
the time was prolonged to 1.5 h from 1 h, the yield enhanced 27%
entry 5). Nevertheless, the yield would come up to 97% when
(
the reaction time was 2 h (entry 6). (3) Compared with the
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jyniu@henu.edu.cn (J.N.).
*E-mail: jpwang@henu.edu.cn (J.W.).
reaction temperature and time, the CO pressure has relatively
■
2
little influence for the yield of COC. The yield just increased by
8
%, when the CO pressure was added to 1.5 MPa from 1.0 MPa
2
(
entry 4). Besides, it appears that, under the same optimal
conditions, the raw material, like P W , Mn(CO) Br, and
2
15
5
ORCID
Co(OAc) ·4H O, showed somewhat low catalytic activity
2
2
Jingyang Niu: 0000-0001-6526-7767
Author Contributions
All authors have given approval to the final version of the
manuscript.
compared with catalyzer 1 (Table S6). The cyclic performance
of catalyst 1 in the reaction was also investigated. 1 was used to
catalyze the cycloaddition of CO for three cycles (entries 8 and
2
9). After three cycles, the carbonyl groups fall from the skeleton
Notes
of POMs, which was shown by a comparison of the IR spectra of
the used and fresh catalysts (Figure S8), indicating that the
catalyst was not relatively stable in this system. Other epoxides
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
(
glycidyl methacrylate/chloromethyloxirane) were then also
examined (entries 10 and 11). The results display that compound
was also activated for these epoxides with the ionic liquid as a
■
We gratefully acknowledge financial support from the Natural
Science Foundation of China (Grants 20771034 and 21401042),
Postdoctoral Science Foundation of Henan Province (Grant
2015031), and 2015 Young Backbone Teachers Foundation
from Henan Province (Grant 2015GGJS-017).
1
cocatalyst.
The mechanism of the cycloaddition of CO and epoxides has
2
30−33
been investigated extensively.
In 2005, the transition-metal-
C
DOI: 10.1021/acs.inorgchem.7b01231
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
(
19) Zhao, J.; Zhao, J.; Ma, P.; Wang, J.; Niu, J.; Wang, J. Manganese
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DOI: 10.1021/acs.inorgchem.7b01231
Inorg. Chem. XXXX, XXX, XXX−XXX