An Organotin Vanadate with Sodalite Topology and Catalytic Versatility in Oxidative Transformations

Article abstract of DOI:10.1002/cctc.201800477

The new coordination polymer formulated as [Et₃SnVO₃] (1) has been synthesized and shown by a combined single-crystal and synchrotron powder X-ray diffraction structural analysis, supported by solid-state NMR, to possess a three-dimensional network structure with the sodalite topology, formed by tetravanadate polyanions, [V₄O₁₂]^4?, that are linked by Et₃Sn⁺ spacers. The catalytic versatility of compound 1 for liquid phase organic reactions was demonstrated by applying it for the epoxidation of olefins, the oxidative dehydrogenation of alcohols, and the oxidation of benzyl alcohol to benzaldehyde and benzoic acid, using tert-butyl hydroperoxide (TBHP) as oxidant. Compound 1 acts a solid reservoir for soluble, catalytically active species, which promote high selectivities to the epoxide and carbonyl (aldehyde/ketone/acid) products. The epoxidation activity compares favorably with those reported for other organotin molybdate, tungstate and vanadate coordination polymers, and is superior to that displayed by the starting materials used for its synthesis (Et₃SnBr and NH₄VO₃) and the metavanadate NBu₄VO₃.

Full text of DOI:10.1002/cctc.201800477

Full Papers
DOI: 10.1002/cctc.201800477
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An Organotin Vanadate with Sodalite Topology and
Catalytic Versatility in Oxidative Transformations
Ana C. Gomes,[a] Margarida M. Antunes,[a] Marta Abrantes,[b, c] Anabela A. Valente,[a] Filipe A.
Almeida Paz,*[a] Isabel S. Gonc¸alves,[a] and Martyn Pillinger*[a]
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The new coordination polymer formulated as [Et3SnVO3] (1) has
been synthesized and shown by a combined single-crystal and
synchrotron powder X-ray diffraction structural analysis, sup-
ported by solid-state NMR, to possess a three-dimensional
network structure with the sodalite topology, formed by
tetravanadate polyanions, [V4O12]4ꢀ, that are linked by Et3Sn+
spacers. The catalytic versatility of compound 1 for liquid phase
organic reactions was demonstrated by applying it for the
epoxidation of olefins, the oxidative dehydrogenation of
alcohols, and the oxidation of benzyl alcohol to benzaldehyde
and benzoic acid, using tert-butyl hydroperoxide (TBHP) as
oxidant. Compound 1 acts a solid reservoir for soluble, catalyti-
cally active species, which promote high selectivities to the
epoxide and carbonyl (aldehyde/ketone/acid) products. The
epoxidation activity compares favorably with those reported for
other organotin molybdate, tungstate and vanadate coordina-
tion polymers, and is superior to that displayed by the starting
materials used for its synthesis (Et3SnBr and NH4VO3) and the
metavanadate NBu4VO3.
24 Introduction
tion polymers) with the goal of obtaining self-supported or
heterogeneous catalysts.[3] MOFs are multidimensional coordi-
nation networks comprised of inorganic secondary building
units (SBUs, metal ions or clusters) spatially separated by
organic linkers. A few vanadium-based MOFs are known and
one of these, V-MIL-57, was shown to be capable of high
activity and selectivity in the epoxidation of cyclohexene with
tert-butyl hydroperoxide (TBHP).[3a–c] The structure of thermally-
25
26 It is well known that homogeneous (molecular) catalysts
27 containing early transition metals (Ti, V, Mo, W and Re) in high
28 oxidation states (IV–VII) can selectively catalyze various types of
29 liquid-phase oxidation reactions such as sulfoxidation and olefin
30 epoxidation.[1] The most effective catalysts are metal-organic
31 complexes in which the active metal center is surrounded by
32 organic (and inorganic) ligands. Vanadium complexes have
33 been found to be particularly efficient catalysts in the oxidation
34 of CꢀH compounds and olefins by H2O2 and other peroxides.[1c,2]
35 Researchers have sought the installation of these active sites
36 within the backbone of metal-organic hybrids (especially metal-
37 organic frameworks (MOFs) or, more widely speaking, coordina-
38
activated V-MIL-47 consists of {VIV-O-VIV} chains of corner-
1
sharing {VO6} octahedra, which are cross-linked by terephtha-
late linkers. Related (albeit non-porous) three-dimensional (3D)
molybdenum oxide-organic frameworks have been prepared by
the linkage of 1D MoVI oxide motifs through suitable bistriazolyl
ligand modules.[4a,b] These compounds were used as (pre)
catalysts for the epoxidation of cis-cyclooctene, the oxidative
dehydrogenation of benzyl alcohol, and the oxidation of
benzaldehyde.[4b,c]
39
[a] Dr. A. C. Gomes, Dr. M. M. Antunes, Dr. A. A. Valente, Dr. F. A. A. Paz,
40
Dr. I. S. Gonc¸alves, Dr. M. Pillinger
Department of Chemistry, CICECO
Aveiro Institute of Materials
University of Aveiro
Campus Universitꢀrio de Santiago, 3810-193 Aveiro, Portugal
E-mail: filipe.paz@ua.pt
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42
All of the metal-organic hybrids referred to above contain
organic linkers. The use of organometallic bridging ligands to
construct metal-organometallic frameworks and coordination
polymers is an underdeveloped area[5] and catalytic applications
have yet to be broadly studied despite the potential synergistic
benefits of an ordered heterobimetallic system.[6] One family of
materials that have attracted attention in this regard are
triorganotin molybdates, tungstates and vanadates, in which
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mpillinger@ua.pt
[b] Dr. M. Abrantes
Centro de Quꢁmica Estrutural
Complexo Interdisciplinar, Instituto Superior Tꢂcnico
Universidade Tꢂcnica de Lisboa
Av. Rovisco Pais, 1, 1049-001 Lisbon, Portugal
[c] Dr. M. Abrantes
2ꢀ
R3Sn+ moieties connect either tetrahedral MO4 groups (M=
Mo, W) or {VV-O-VV} chains to form 1D, 2D or 3D network
Present address:
KIC InnoEnergy - International Affairs Office
Instituto Superior Tꢂcnico
Universidade Tꢂcnica de Lisboa
Av. Duque de ꢃvila, 23–18 Esq., 1000-138 Lisbon, Portugal
1
structures. The structures are very much dependent on the
nature of the substituent R and the Sn/M molar ratio (M=V,
Mo, W).[7] With R=Me, M=Mo (or W) and Sn/M=1, anionic
coordination polymers of the type [(Me3Sn)MO4]ꢀ are formed in
which Me3SnO2 bipyramides are linked with MO4 tetrahedra to
form chains.[8] For Sn/M=2, i.e. [(Me3Sn)2MO4], all four of the M-
bonded oxygens are linked to Me3Sn+ groups, resulting in a
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/cctc.201800477
This manuscript is part of a Special Issue on the “Portuguese Conference on
Catalysis” based on the International Symposium on Synthesis and Catalysis
(ISySyCat).
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layered structure.[9] Catalytic investigations with these com-
below), their chemical equivalence together with considerable
structural disorder account for why only single peaks are
observed for each type of carbon atom.
˜
pounds were first described by Abrantes, Gonc¸alves and Romao
and co-workers.[10] The 2:1 derivatives [(R3Sn)2MO4] (M=Mo, W;
R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) were examined
for the oxidation of benzothiophene[10a] and the epoxidation of
olefins.[10b,c] Catalytic performance was strongly affected by the
nature of M and the tin-bonded R groups, the type of oxidant
used (H2O2 or TBHP), and the addition of cosolvents. One of the
most catalytically active systems for both reactions comprised
The IR and Raman spectra of compound 1 are consistent
with the presence of cyclic tetranuclear [V4O12]4ꢀ clusters in the
structure (Figure S2). In the Raman spectrum, the bands at 953
and 918 cmꢀl, with strong and medium intensity, respectively,
may be assigned to symmetric stretching vibrations, nsym(VO2),
of the two shortest VꢀO (terminal V=O character) bonds, i.e.
those linked to Et3Sn+ cations. The same modes appear to
originate weak-medium IR bands at 963 and 913 cmꢀ1. These
assignments are made on the basis of previous assignments
made for the tetrametavanadate anion.[17] According to these
previous assignments, the very strong band at 807 cmꢀ1 in the
IR spectrum of 1 is due to the IR-active mode arising from the
asymmetric stretching of these groups, nasym(VO2); the weak
Raman band at 863 cmꢀ1 may be due to the Raman-active
component arising from this mode. A strong band due to a
VꢀOꢀV stretching mode, nasym(VꢀOꢀV), is found at 672 cmꢀ1 in
the IR spectrum. In the region of the VꢀO stretching vibrations
10 the tri-n-butyltin molybdate as catalyst, aqueous H2O2 as
11 oxidant and a chlorinated cosolvent. The compounds [(nBu3Sn)2
12 MO4] (M=Mo, W) were subsequently used as recyclable
13 heterogeneous catalysts for the oxyfunctionalization of mono-
14 terpenes,[11] N-oxidation of primary and secondary amines,[12]
15 and the synthesis of hexahydroquinoline and 1,4-dihydropyr-
16 idine derivatives.[13] The high activity and selectivity of
17 [(nBu3Sn)2MoO4] for the transesterification of diethyl carbonate
18 and various alcohols was attributed to a synergistic effect
19 between the groups of MoO42ꢀ and Bu3Sn+ in the catalyst.[14]
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Catalytic studies with the trimethyltin vanadate [Me3SnVO3]
21 indicated that it was a more efficient catalyst than [(nBu3Sn)2
22 MoO4] for the epoxidation of olefins with TBHP.[15] The
23 trimethyltin vanadate has a 3D network structure comprising
24 infinite metavanadate chains which are linked by Me3Sn+
25 cations.[16] Given that the tin-bonded R groups in organotin
26 metalates have a strong structure-directing (and hence cata-
27 lytic) influence, we undertook the synthesis of the triethyltin
28 analogue, [Et3SnVO3], which has not been previously reported.
29 Herein we describe the structural elucidation of this compound
30 and an examination of its catalytic performance for the
31 epoxidation of olefins and the oxidation of alcohols.
32
the IR spectrum of
1 closely resembles those reported
previously for several hybrid materials containing metal-
phenanthroline complexes and [V4O12]4ꢀ rings.[18] Zurkova et al.
proposed slightly different band assignments, namely nsym(VO2)
and nasym(VO2) for the high-frequency (>900 cmꢀ1) bands,
nasym(VꢀOꢀV) for the band around 810 cmꢀ1, and nsym(VꢀOꢀV)
for the band around 670 cmꢀ1.[18]
ˇ
´
´
For 1, the Raman-active n(SnC) vibration appears at
486 cmꢀ1 and is in agreement with literature results for the
coordination polymer [(Et3Sn)3Co(CN)6].[19] A second, consider-
ably weaker, Raman band at 523 cmꢀ1 is assigned to one of the
asymmetric (with respect to the SnC3 fragment) stretching
modes which appears more clearly in the IR spectrum at the
same frequency.[19]
33
34 Results and Discussion
35
36 Synthesis and Structural Elucidation
37
38 The organotin vanadate [Et3SnVO3] (1) was obtained in near-
39 quantitative yield as an analytically pure pale yellow polycrystal-
40 line precipitate after addition of an acetone solution of Et3SnBr
41 to a solution of NH4VO3 in water [Eq. (1)].
42
A full structure description of 1 was achieved through a
combination of single-crystal and synchrotron high-resolution
powder X-ray diffraction (XRD) studies. Single-crystals were
obtained by dissolving 1 in DMF, followed by layering the
resultant solution with pentane (middle layer) and diethyl ether
(top layer). The compound crystallizes in the cubic F-43c space
group (Table 1), exhibiting a considerable structural disorder for
the Sn-bound ethyl moieties, and some solvent accessible
volume that could not be unequivocally modelled because of a
considerable smeared-out electron density. The homogeneity of
the bulk material was unequivocally confirmed from Rietveld
refinement using high-resolution powder XRD data as depicted
in Figure 1. The combined study clearly shows that the
presented model describes well the structural features of 1,
with the missing electron density contributing mostly to the
overall background of the XRD data.
(1)
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The vanadium (V5+) environment in 1 was investigated by
46 51V MAS NMR spectroscopy (Figure S1 in the Supporting
47 Information). A single isotropic peak is observed at d=
48 ꢀ666.3 ppm, indicating the existence of one type of V5+ site.
49 Similarly, the presence of one type of Et3Sn group is indicated
50 by the 119Sn HPDEC MAS NMR spectrum, which shows one fairly
51 sharp resonance at d=74.3 ppm, and the 13C{1H} CP MAS NMR
52 spectrum, which shows two peaks at d=10.5 and 12.6 ppm for
53 the Sn-bonded ethyl groups (Figure S1). These results point to
54 the presence of single crystallographically unique V and Sn sites
55 in the crystal structure of 1. Although the crystal structure
56 solution shows that the three CH2 and three CH3 groups in each
57 Et3Sn+ cation are not crystallographically equivalent (see
The asymmetric unit of 1 is composed of just two metal
centers as shown in Figure 2. Sn1 exhibits a distorted {SnC3O2}
trigonal bipyramidal coordination environment in which the
equatorial plane is formed by the disordered ethyl moieties and
the apical positions are occupied by oxygen atoms from
[V4O12]4ꢀ tetrameric units [internal polyhedral angle close to
being linear - 178.5(9)8]: while the SnꢀO distances were found
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in the 2.204(8)-2.311(10) A range, all SnꢀC bond lengths are
Table 1. Crystal and structure refinement data for [Et3SnVO3] (1).
˚
identical to 2.145(12) A (see Table 2 for details – this occurs
Formula
C6H15O3SnV
because of the structural constraints imposed in the single-
crystal XRD modeling so as to ensure chemically reasonable
geometries for these disordered moieties). The structural model
has one position for the ethyl groups significantly more favored
with a rate of occupancy of 83(2) %. We emphasize that this
may change from crystal to crystal since for the powder XRD
studies the rates had to be slightly adjusted to a ratio of ca.
3 : 2 to better fit the data. V1 exhibits a typical tetrahedral {VO4}
coordination environment with the VꢀO distances ranging from
Formula weight
Crystal system
Space group
304.81
Cubic
F-43c
30.565(4)
˚
a [A]
3
˚
Volume [A ]
28554(10)
Z
96
1.702
2.853
Dc [gcmꢀ3
]
m(Mo-Ka) [mmꢀ1
]
Crystal size [mm]
Crystal type
0.31ꢁ0.28ꢁ0.21
Yellow block
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q range
3.77 to 25.35
Index ranges
ꢀ36ꢁhꢁ21, ꢀ35ꢁkꢁ29, ꢀ35ꢁlꢁ13
˚
1.593(10) to 1.736(19) A, and the tetrahedral internal angles
Reflections collected
Independent reflections
Completeness to q=25.248
Final R indices [I>2s(I)][a,b]
Final R indices (all data)[a,b]
Weighting scheme[c]
Largest diff. peak and hole
16543
2132 [Rint =0.0594]
97.5%
from 106.9(5) to 115.4(16)8 (Table 2). This tetrahedral building
unit is corner-shared with three symmetry-related ones to form
a [V4O12]4ꢀ tetrameric moiety as depicted in Figure 2b and 2d.
The crystal structure of 1 is constructed by bridges between
[V4O12]4ꢀ tetrameric moieties via the distorted {SnC3O2} trigonal
R1=0.0742, wR2=0.1913
R1=0.0937, wR2=0.2103
m=0.1390
ꢀ3
˚
2.115 and ꢀ0.477 eA
[a]
bipyramidal Sn environments, ultimately forming
a
supramolecular cage as depicted in Figure 3a. These connec-
tions are ensured by the O1 and O3 oxygen atoms of the
crystallographically independent {VO4} coordination environ-
ment, which imposes some local stress in the overall geometry
which is ultimately reflected by the smallest tetrahedral
O3ꢀV1ꢀO2 angle of 115.4(16)8 (Figure 2b and Table 2). The
{[Et3Sn]12[V4O12]6}12ꢀ supramolecular cage (the ꢀ12 charge arises
because this formula accounts for a total of 24 fully-occupied
inter-cage connecting oxygen atoms) contains empty space at
the center which is most likely occupied by solvent molecules.
As shown in Figure 3a, this void is surrounded by ethyl groups
and, therefore, is of hydrophobic nature. The impossibility of
establishing strong supramolecular interactions with the even-
tually confined solvent molecules further explains the smeared-
out electron density registered in the XRD studies.
The interconnection between [V4O12]4ꢀ tetrameric moieties
and the bridging Et3Sn+ spacers leads to the formation of a
truly unprecedented, high-symmetry 3D hybrid network as
depicted in the inset of Figure 1. A search in the literature and
in the Cambridge Structural Database (CSD Version 5.38 with 3
updates)[20] reveals the existence of only a handful of organotin
vanadate compounds in the literature. Although the majority
are discrete complexes,[21] a number of polymeric structures
have also been reported: two 1D chain-type polymers reported
by Herntrich & Merzweiler ([(Ph3Sn)3VO4]·CH3CN and [(Ph3Sn)3
VO4]·2DMF);[22] two 3D compounds (just like 1) originally
[b]
[c]
where
˚
Table 2. Bond distances (in A) and angles (in degrees) for the distorted
trigonal bipyramidal {SnC3O2} coordination environment and the tetrahe-
dral V5+ site in [Et3SnVO3] (1).[a]
Sn1ꢀO1
Sn1ꢀO3i
2.204(8)
2.311(10)
O1ꢀSn1ꢀO3i
V1ꢀO1ꢀSn1
V1iiiꢀO2ꢀV1
V1ꢀO3ꢀSn1iv
178.5(9)
141.0(5)
160.9(8)
156.3(9)
Disordered carbon atoms (see Figure 2 for details):
83(2) %
17(2) %
Sn1ꢀC1
Sn1ꢀC5
Sn1ꢀC7
2.145(12)
2.145(12)
2.145(12)
97.7(10)
81.9(9)
117.2(12)
88.9(11)
92.5(10)
105.8(12)
136.2(12)
93.0(10)
85.7(9)
Sn1ꢀC2
2.145(12)
2.145(12)
2.145(12)
109(3)
72(2)
112.5(19)
90(2)
91(2)
109.7(16)
135(3)
85.0(16)
93.5(16)
Sn1ꢀC4
Sn1ꢀC8
C1ꢀSn1ꢀO1
C1ꢀSn1ꢀO3i
C5ꢀSn1ꢀC1
C5ꢀSn1ꢀO1
C5ꢀSn1ꢀO3i
C7ꢀSn1ꢀC1
C7ꢀSn1ꢀC5
C7ꢀSn1ꢀO1
C7ꢀSn1ꢀO3i
C2ꢀSn1ꢀO1
C2ꢀSn1ꢀO3i
C4ꢀSn1ꢀC2
C4ꢀSn1ꢀO1
C4ꢀSn1ꢀO3i
C8ꢀSn1ꢀC4
C8ꢀSn1ꢀC2
C8ꢀSn1ꢀO1
C8ꢀSn1ꢀO3i
described by Rosenland
& Merzweiler ([Me3SnVO3] and
[(Me2Sn)4V2O9]),[16] with the former being more recently redeter-
mined and studied by us.[15] In this context, compound 1 stands
out as a truly unique material with a topology similar to that of
a known mineral (see below). The Sn-bound organic moiety
seems to have some influence on the isolated structure: while
bulky ligands such as phenyl seem to promote the formation of
low-dimensional structures (i.e., 1D), aliphatic ligands allow the
polymerization into 3D frameworks; in addition, although the
number of comparable structures is small, one can infer that
the size of small aliphatic chains (methyl or ethyl groups) does
not have any influence on this type of dimensionality since for
both cases 3D frameworks were isolated.
V1ꢀO1
V1ꢀO2ii
V1ꢀO2
V1ꢀO3
1.659(8)
O1ꢀV1ꢀO2
O1ꢀV1ꢀO2ii
O2iiꢀV1ꢀO2
O3ꢀV1ꢀO1
O3ꢀV1ꢀO2
O3ꢀV1ꢀO2ii
109.7(16)
109.6(17)
107.5(7)
106.9(5)
115.4(16)
107.6(14)
1.711(19)
1.736(19)
1.593(10)
[a] Symmetry transformations used to generate equivalent atoms: (i) y,
ꢀx+1.5, ꢀz+2; (ii) ꢀx+1.5, zꢀ0.5, ꢀy+1.5; (iii)ꢀx+1.5, ꢀz+1.5, y+0.5;
(iv) ꢀy+1.5, x, ꢀz+2.
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Figure 1. Final Rietveld plot (synchrotron XRD data) of [Et3SnVO3] (1) (Debye-Scherrer geometry, 2q range: 1.000-22.000, 110 K). Observed data points are
indicated as a blue line, the best fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid red and grey lines, respectively. Green
vertical bars indicate the angular positions of the allowed Bragg reflections for 1. The inset depicts a perspective view along the [100] direction of the unit cell
P
yi;o ꢀyi;c
j
j
i
P
of 1. Refinement details: Zero shift [2q8]=ꢀ0.006(2)8; 344 independent reflections; 36 global refined parameters; Rp
¼
¼ 8:06;
yi;o
j
j
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P
i
P
2
u
w
y
i;oꢀyi;c
In;o ꢀIn;c
i ð
Þ
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
j
j
u
t
ðnꢀpÞ
i ð i;o
Rwp
Rexp
i
n
P
P
P
Rwp
¼
¼ 7:72; Rexp
¼
¼ 5:08; GOF ¼
¼ 1:52; RBragg
¼
¼ 7:13 where yi,o and yi,c are the observed and calculated profile
2
2
In;o
w
y
w
y
i ð i;o
Þ
Þ
n
i
i
intensities, In,o and In,c the observed and calculated intensities, respectively. The summations run over i data points or n independent reflections. Statistical
weights wi are usually taken as 1/yi,o.
Following the recommendations of Alexandrov et al.,[23] who
suggested that any moiety (ligand, atom or clusters of atoms)
connecting more than two metal centers (mn) should be
considered as a network node, 1 is a uninodal 4-connected
network (node: the V5+ metal center) with a Schafli point
¨
symbol of {42·64} as revealed by the software package TOPOS.[24]
As represented in Figure 3b, the internodal distances vary
4ꢀ
˚
between 3.399(5) A (for the V···V distance within the [V4O12]
˚
tetrameric moieties) and 7.450(3) A (for the bridge across the
Et3Sn+ spacers). Remarkably, 1 shares the topology with the
well-known mineral sodalite (sod), with the crystal structure
(inset in Figure 1) being described by the close packing of
sodalite-like cages as shown in Figure 4.
The thermal stability of compound 1 was studied by
thermogravimetric analysis under air (Figure S3 in the Support-
ing Information). Decomposition of the Sn-bonded ethyl groups
begins at 1608C and leads to a very abrupt (DTGMAX =2108C)
mass loss of 19.8% up to 2208C, followed by a more protracted
loss of about 10% in overlapping steps between 220 and
5008C.
Investigation of the particle morphology of 1 by scanning
electron microscopy (SEM) revealed aggregates of irregular
flakelike particles (Figure S4 in the Supporting Information).
Figure 2. Schematic representation of the (a) Sn4+ and (b) V5+ crystallo-
graphically independent coordination environments present in [Et3SnVO3] (1)
resembling, respectively, a distorted trigonal bipyramid and a distorted
tetrahedron. (c) and (d) Top views of the same {SnC3O2} and {VO4}
coordination environments. Selected bond lengths and angles are given in
Table 2. Symmetry transformations used to generate equivalent atoms have
been omitted for clarity.
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Catalytic Studies
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The catalytic performance of 1 was investigated for the
epoxidation of cis-cyclooctene (Cy8) with TBHP, without
cosolvent, at 558C. Cyclooctene oxide (CyO) was the only
product formed with 82% yield at 24 h reaction (Table 3). This
performance is on a par with those reported previously for
organotin molybdates [(R3Sn)2MoO4(H2O)n] (R3 =(Me)2(menthyl)
or nBu3) used under equivalent reaction conditions (Ta-
ble 4).[10b,26] The trimethyltin vanadate [Me3SnVO3] led to a
slightly lower epoxide yield of 65% at 24 h for the Cy8 reaction
with TBHP.[15] Compound 1 exhibited superior catalytic perform-
ance to the starting materials used for its synthesis (Et3SnBr,
negligible Cy8 conversion; NH4VO3, 1% CyO selectivity at 32%
conversion) and the metavanadate NBu4VO3 (84% CyO selectiv-
ity at 42% conversion). These results suggest that the active
species of 1 contain vanadium(V) in a favorable coordination
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Table 3. Reactions of olefins and alcohols with TBHP in the presence of 1,
at 558C.
Substrate
Cosolvent
Conv.
[%][a]
Select.
[%][b]
Olefins
cis-cyclooctene
none
82 (82)[c]
78
73
65
65
23
100 (100)[c]
100
100
100
93
100
1,2-dichloroethane
hexane
acetonitrile
none
cyclododecene
1-octene
none
trans-2-octene
(R)-(+)-limonene
a-pinene
none
none
none
45
68
50
100
85[d]
67
Alcohols
cyclooctanol
cyclohexanol
1-cyclohexylethanol
sec-phenethyl alcohol
benzyl alcohol
none
none
none
none
none
68
55
45
62
78
94
100
96
98
24
Figure 3. (a) Schematic representation of the sodalite-like {[Et3Sn]12[V4O12]6}12ꢀ
supramolecular cage formed by the interconnection between corner-shared
tetramers, [V4O12]4ꢀ, and Et3Sn+ spacers. (b) Simplified topological construc-
tion of the same sodalite-like cage in which the m2 bridges formed by the
[a] Substrate conversion at 24 h reaction. [b] Selectivity to the corresponding
epoxide in the case of the olefins, and carbonyl (aldehyde/ketone)
Et3Sn+ spacers have been removed [internodal distance of 7.450(3) A].
˚
[c]
products in the case of the alcohols.
are for the used catalyst.
Catalytic results in parentheses
[d]
Selectivity to 1,2-limonene oxide. The
corresponding 1,2-epoxide, 8,9-epoxide and 1,2:8,9-diepoxide products
were formed in a molar ratio of 1:0.09:0.09.
Table 4. Cyclooctene epoxidation in the presence of organotin metalate
compounds.[a]
Catalyst
Cy8 Cat. Load
MR
Conv. Ref.
[%][b]
ꢀ1
[M]
[gcat Lmix
]
[Et3SnVO3] (1)
3.6
5.7
1:130:200 82
This
work
[15]
[26]
[10b]
[10b]
[Me3SnVO3]
3.5
3.7
2.7
2.7
2.3
19.1
15
1:400:640 65
[c]
[(R3Sn)2MoO4(H2O)3.5
[(nBu3Sn)2MoO4]
[(nBu3Sn)2WO4]
]
1:100:150
~85
1:100:200 88
1:100:200 30
16.7
[a] Reaction conditions: oxidant=5.5 M TBHP in decane, 558C, no cosolvent.
Other experimental conditions shown for comparison are initial molar
concentration of Cy8, catalyst load (expressed as initial mass of organotin
compound per total volume of reaction mixture), and initial catalyst:-
Figure 4. Crystal packing of cubic [Et3SnVO3] (1) represented by the
interconnection between adjacent sodalite-like cages. Representation cre-
ated using the software package Systre.[25]
[b]
Cy8:TBHP molar ratio (MR). Cy8 conversion at 24 h. Epoxide selectivity
[c]
was 100% in all cases. R3Sn=(Me)2(menthyl)Sn.
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1
2
3
4
5
6
7
8
9
environment for the catalytic epoxidation reaction. The reaction
mechanism may involve the coordination of the Lewis base
hydroperoxide oxidant to the Lewis acid metal center (activat-
ing the peroxidic oxygen atom), and an oxygen atom transfer
reaction from the oxidizing species to the olefin.[27]
endocyclic double bond relative to the (less hindered, but
electron poorer) exocyclic one. The reaction of Pin with TBHP in
the presence of 1 gave a-pinene oxide with 67% selectivity at
50% conversion. A complex mixture of reaction products was
obtained, although these results are fairly good considering the
high reactivity of a-pinene oxide.
The addition of a cosolvent to the reaction mixture affected
the catalytic performance of 1 (Figure 5, Table 3): the reaction
rate (based on conversion at 50 min reaction) decreased in the
order: no cosolvent (29%) >1,2-dichloroethane (19%)ꢂhexane
Compound 1 was further explored as a catalyst for the
oxidation of alcohols, namely cyclooctanol, cyclohexanol, 1-
cyclohexylethanol, sec-phenethyl alcohol and benzyl alcohol, at
558C (Table 3). Apart from benzyl alcohol, the corresponding
aldehyde/ketone products were formed in high selectivity (94-
100% selectivity at 45–68% conversion, 24 h reaction). No
reaction occurred without TBHP, indicating that the dehydro-
genation of the alcohols is an oxidative process. To the best of
our knowledge, this is the first report of oxydehydrogenation
activity of an organotin metalate for the reaction of alcohols
with a hydroperoxide oxidant to give carbonyl products. The
reaction of benzyl alcohol in the presence of 1 led to
benzaldehyde and benzoic acid with 24% and 72% selectivity,
respectively, at 78% conversion, indicating the ability of 1 for
the cascade reaction of alcohol-to-aldehyde-to-carboxylic acid.
For 1, the reaction mixtures were always biphasic solid-
liquid. The solid catalyst was separated from the Cy8 reaction
mixture by filtration (at 24 h reaction) and used in a second run
(after washing with n-pentane and drying at room temperature
overnight). The recovered solid led to similar catalytic results to
the fresh catalyst, suggesting that 1 is fairly stable (Figure 6,
Table 3). On the other hand, a hot filtration test (details in the
experimental section) for 1 led to similar catalytic results to
those for a normal catalytic test (without catalyst filtration),
indicating that the reaction occurred in homogeneous phase
(Figure 6). The elemental composition of the solid phase
recovered in the hot filtration test was semi-quantitatively
analyzed by energy dispersive X-ray spectroscopy (EDS), and
10 (17%)>CH3CN (8%). Possibly, the catalyst’s acidity is levelled
11 off by the Lewis basic CH3CN and/or these molecules compete
12 with the reagents for coordination to the metal center, leading
13 to slower reaction kinetics.
14
The olefin substrate scope was expanded to other cyclic
15 and linear olefins, and unsaturated terpenes: cyclododecene
16 (Cy12), 1-octene (1nC8), trans-2-octene (2nC8), (R)-(+)-limonene
17 (Lim) and a-pinene (Pin) (Table 3). Steric effects seemed to be
18 important for Cy12 since the reaction with this substrate was
19 slower than with (less bulky) Cy8: 65% and 82% conversion for
20 Cy12 and Cy8, respectively, at 24 h reaction. For the linear C8
21 olefins 1nC8 and 2nC8, the corresponding epoxides were
22 always the only reaction products. On the basis of the
23 mechanistic points mentioned above, the higher reactivity of
24 2nC8 in comparison to 1nC8 is likely due to electronic effects,
25 which may offset any steric disadvantage arising from the
26 internal location of the double bond. The double bond of 2nC8
27 possesses greater electronic density than that of 1nC8, and
28 thus the former may be more susceptible to electrophilic attack
29 by an oxidizing species, leading to a faster epoxidation reaction.
30 This hypothesis is supported by the catalytic results for Lim as
31 substrate, which possesses terminal and endocyclic double
32 bonds. The main reaction product was 1,2-limonene oxide
33 (85% selectivity at 68% conversion), and limonene diepoxide
34 was formed with 8% selectivity. These results demonstrate a
35 high regioselectivity in favor of the epoxidation of the
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Figure 6. Hot filtration test carried out for 1 in the epoxidation of Cy8 with
TBHP, at 558C (ꢁ), and comparison with the reaction of Cy8 under normal
conditions without filtration of the solid catalyst (first run (*); second run
(&)). CyO selectivity was always 100%.
55
56
57
Figure 5. Kinetic profiles of the epoxidation of Cy8 with TBHP in the
presence of 1, without a cosolvent (*), or using 1,2-dichloroethane (+), n-
hexane (&) or CH3CN (ꢁ) as cosolvent, at 558C.
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graphite monochromator and a flat plate sample holder, in a
Bragg-Brentano para-focusing optics configuration (40 kV, 50 mA).
Samples were step-scanned in the range from 3.5 to 708 2q with
steps of 0.028 and a counting time of 25 s per step. Thermogravi-
metric analyses were performed under air using a Shimadzu TGA-
50 system with a heating rate of 58Cminꢀ1. SEM images were
collected using a Hitachi SU-70 microscope operating at 15 kV.
Samples were prepared by deposition on aluminum sample holders
followed by carbon coating using an Emitech K 950 carbon
evaporator. EDS data were collected using the same electron
microscope while employing a Bruker Quantax 400 microanalysis
system.
1
2
3
4
5
6
7
8
9
the results were compared with those obtained for as-
synthesized 1. In both cases a Sn/V molar ratio of ca. 0.9 was
obtained, and the elemental spectra were similar (Figure S5 in
the Supporting Information). These results suggest that the
elemental composition of 1 (i.e. Sn/V=1) was retained for the
dissolved metal species. The filtrate obtained from the hot
filtration test of 1 at 40 min reaction was analyzed by ICP-OES,
which indicated that ca. 24 mol% of the initial amount of 1 had
dissolved. This corresponds to a catalyst solubility of ca.
10 4.5 mM, and an initial turnover frequency (TOF) of ca.
11 252 molmolꢀ1V hꢀ1, which is more than double that reported
12 previously for the trimethyltin vanadate [Me3SnVO3] (82 mol
13 molꢀ1V hꢀ1),[15] and at least an order of magnitude greater than
14 those for [(nBu3Sn)2MO4] (M=Mo, W)[10b] and [((Me)2(menthyl)
15 Sn)2MoO4(H2O)3.5],[26] tested as catalysts in the same reaction.
16
FT-IR spectra were collected using KBr (Aldrich 99%, FT-IR grade)
pellets on a Mattson-7000 infrared spectrophotometer. FT-Raman
spectra were recorded on a Bruker RFS 100 spectrometer with a
Nd:YAG coherent laser (l=1064 nm). 13C, 51V and 119Sn solid state
NMR spectra were recorded at 100.62, 105.24 and 149.21 MHz,
respectively, on a Bruker Avance 400 spectrometer (9.4 T). 1H-13C
cross-polarization (CP) MAS NMR spectra were acquired with a
17
1
spinning rate of 7 kHz, 4.5 ms H 908 pulses, 2 ms contact time and
18 Conclusions
19
4 s recycle delays. 51V MAS NMR spectra were recorded with a
spinning rate of 14 kHz, short 0.6 ms (equivalent to 108) pulses and
5 s recycle delays. 119Sn CP MAS NMR spectra were recorded with a
spinning rate of 15 kHz, 3.5 ms 1H 908 pulses, a contact time of 3 ms
and 4 s recycle delays. Chemical shifts are quoted in parts per
million (ppm) from SiMe4 (13C), VOCl3 (51V) and SnMe4 (119Sn).
20 The successful synthesis and structural elucidation of the
21 coordination polymer [Et3SnVO3] (1) has provided an excellent
22 opportunity to examine the structure-directing role of the tin-
23 bonded groups by comparison with the known polymer
24 [Me3SnVO3]. In both compounds metavanadate subunits are
25 linked by R3Sn+ cations to form 3D network structures.
26 However, while in [Me3SnVO3] the metavanadate subunit
27 consists of infinite chains of corner-sharing {VO4} tetrahedra, in
Synthesis of [Et3SnVO3] (1)
NH4VO3 (0.58 g, 5 mmol) was dissolved in water (40 mL) by stirring
and heating the suspension to 608C for 15 min. A solution of
Et3SnBr (1.43 g, 5 mmol) in acetone (5 mL) was added dropwise to
the stirred solution of NH4VO3, resulting in the immediate formation
of a precipitate. After stirring the mixture for a further 30 min, the
solid product was filtered, washed thoroughly with water and dried
overnight at 1008C to give compound 1 (1.50 g, 99%) as a pale
yellow powder. Anal. Calcd for C6H15O3SnV (304.83): C, 23.64; H,
4.96%. Found: C, 23.76; H, 5.04. FT-IR (KBr, cmꢀ1): n=2965 (m), 2946
(m), 2918 (m), 2868 (m), 2821 (w), 2732 (w), 1455 (m), 1419 (w),
1377 (w), 1234 (w), 1187 (w), 1020 (w), 963 (w), 913 (sh), 875 (sh),
807 (vs), 672 (s), 523 (m), 492 (sh), 365 (w). Raman (cmꢀ1): n=2944
(m), 2915 (vs), 2870 (m), 2819 (vw), 2733 (vw), 1457 (w), 1420 (w),
1378 (w), 1192 (m), 953 (vs), 918 (m), 863 (w), 566 (w), 523 (w), 486
(s), 444 (m), 367 (w), 251 (m). 13C CP MAS NMR: d=12.6 (CH2CH3),
10.5 (CH2CH3) ppm. 119Sn CP MAS NMR: d=74.3 ppm. 51V MAS NMR:
d=ꢀ666.3 ppm.
28
1
the subunit is the cyclic tetranuclear anion [V4O12]4ꢀ.
29 Compound 1 is the first example of an organotin metalate with
30 the sodalite topology. Interesting results were obtained when
31 using 1 as a catalyst in oxidative transformations with tert-butyl
32 hydroperoxide as oxidant. Under the reaction conditions used,
33 1 acts a solid reservoir for soluble, catalytically active species,
34 which promote high selectivities in the epoxidation of olefins
35 and the oxidation of alcohols to give carbonyl products. The
36 intrinsic activity (TOF) for the reaction of the model substrate
37 cis-cyclooctene compares favorably with values determined for
38 other organotin metalates. We conclude that 1 is a promising
39 catalyst for oxidative transformations and that other interesting
40 catalytic materials may be found by expanding the family of
41 hybrid organotin vanadates, which to date is limited to only a
42 handful of compounds.
Single-Crystal X-ray Diffraction Studies
43
44
Single crystals of [Et3SnVO3] (1) were manually harvested from the
crystallization vial and immersed in highly viscous FOMBLIN Y
perfluoropolyether vacuum oil (LVAC 140/13, Sigma-Aldrich) to
avoid degradation caused by evaporation of the solvent.[28] Crystals
were mounted on Hampton Research CryoLoops with the help of a
Stemi 2000 stereomicroscope equipped with Carl Zeiss lenses. X-
ray diffraction data were collected at 180(2) K on a Bruker D8
45 Experimental Section
46
47 Materials and Methods
48
Ammonium metavanadate (Fluka), triethyltin chloride (Alfa Aesar),
acetone (99.5%, Fluka), dimethylformamide (99%), n-pentane
(99%), 1,2-dichloroethane (99%), n-hexane (99%), diethyl ether
(99.8%), acetonitrile (99.9%) and 5–6 M TBHP in decane were
acquired from Sigma-Aldrich unless otherwise indicated, and used
as received.
49
˚
50
51
52
53
54
55
56
57
QUEST equipped with a Mo-Ka (l=0.71073 A) sealed-tube X-ray
source, a multilayer TRIUMPH X-ray mirror, a PHOTON 100 CMOS
detector, and an Oxford Instruments Cryostream 700+ Series
cooler.
Diffraction images were processed using the software package
SAINT+,[29] and data were corrected for absorption by the multi-
scan semi-empirical method implemented in SADABS.[30] The
structure was solved using the algorithm implemented in SHELXT-
Microanalyses for C, H and N were carried out with a Truspec Micro
CHNS 630-200-200 elemental analyzer. Routine X-ray powder
diffraction data were collected on an X’Pert MPD Phillips diffrac-
˚
tometer (Cu-Ka X-radiation, l=1.54060 A) fitted with a curved
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2014,[31] which allowed the immediate location of almost all of the
heaviest atoms composing the molecular unit. The remaining
missing and misplaced non-hydrogen atoms were located from
difference Fourier maps calculated from successive full-matrix least-
squares refinement cycles on F2 using the latest SHELXL from the
2014 release.[32] All structural refinements were performed using
the graphical interface ShelXle.[33]
counts of six detectors (covering roughly 5.58 2q) were rebinned
and normalized to give the equivalent step scans (0.0028) suitable
for further structural analyses.
1
2
3
4
5
6
7
8
9
The collected high-resolution powder XRD pattern was indexed
using the LSI-Index algorithm implemented in TOPAS-Academic
V5,[36] and
a whole-powder-pattern Pawley fit unequivocally
confirmed once again the cubic F-43c space group as being the
most suitable. The crystal structure was determined in TOPAS-
Academic V5[36a] by using a simulated annealing approach. Rietveld
structural refinements[37] were performed in the same programme
using a Chebychev polynomial throughout the entire angular range
to model the background contribution, and using the atomic
coordinates as provided from the single-crystal XRD studies
performed (see previous section). Atomic coordinates were allowed
to refine against the powder data with virtually the same structure
being derived from both models. A modified Thompson-Cox-
Hastings pseudo-Voigt (TCHZ) profile function was selected to
generate the line shapes of the simulated diffraction peaks.[38]
Although the inorganic backbone of 1 could be unequivocally
located and refined anisotropically, the three crystallographically
independent ethyl groups bound to tin atoms were found to be
considerably affected by thermal disorder. Each moiety was found
to be, at least, disordered over two crystallographic locations. The
final structural model contemplated the existence of two sets of
locations for the three independent moieties which were refined
with complementary rates of occupancy that, ultimately, refined to
83(2) and 17(2) % (please see Figure 2 for additional details). These
moieties were refined with the geometry heavily restrained to
guarantee chemical reasonableness. Hydrogen atoms bound to
carbon were placed at their idealized positions using appropriate
HFIX instructions in SHELXL: 23 for the ꢀCH2ꢀ moieties and 33 for
the terminal methyl groups. These hydrogen atoms were included
in subsequent refinement cycles with isotropic thermal displace-
ment parameters (Uiso) fixed at 1.2 or 1.5ꢁUeq of the parent atoms,
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Catalysis
The catalytic reactions were carried out at 558C under air
atmosphere, using batch reactors (5 mL capacity) equipped with a
magnetic stirrer and a valve for sampling. The reactor was loaded
with the catalyst [Et3SnVO3] (1) (28 mmol), substrate (3.6 mmol) and
ca. 5.5 mmol tert-butyl hydroperoxide (ca. 5.5 M in decane). The
reactions were typically carried out without additional solvent
(other than the decane present in the TBHP solution). For the
substrate Cy8, the reaction was also carried out using a cosolvent
(1 mL), namely 1,2-dichloroethane, n-hexane or acetonitrile. Sam-
ples were withdrawn periodically and analyzed using a Varian 3800
GC equipped with a capillary column (DB-5, 30 mꢁ0.25 mm for the
reactions of the olefins, and CP WAX 52CB, 30 mꢁ0.53 mm for the
reactions of the alcohols) and a FID detector. The products were
quantified using calibration curves with n-nonane or undecane as
internal standard (added after the reaction). The reaction products
were identified by GC-MS [Trace GC 2000 Series (Thermo Quest CE
Instruments) - DSQ II (Thermo Scientific), equipped with a capillary
DB-1 column (30 m ꢁ 0.25 mm; 0.25 mm) and using He as carrier
gas]. A hot filtration test was carried out for 1 as follows: the
reaction mixture was filtered at 40 min reaction and 558C, using a
0.2 mm PTFE membrane, and subsequently the filtrate was left to
react further at 558C.
respectively. The final structural model contains approximately
3
2564 A of solvent-accessible volume as revealed by PLATON.[34]
˚
These voids contain a considerable smeared-out electron density
that prevented a proper modelling of the potential solvent
contained therein. The last difference Fourier map synthesis
showed the highest peak (2.115 eAꢀ3) and the deepest hole
˚
ꢀ3
˚
˚
(ꢀ0.477 eA ) located at 0.02 and 0.96 A from Sn1 and H4B,
respectively.
Structural drawings were created using Crystal Impact Diamond.[35]
CCDC-1828416 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via http://www.ccdc.ca-
m.ac.uk/data request/cif.
Synchrotron Powder X-ray Diffraction Studies
High-resolution powder synchrotron X-ray diffraction data for
[Et3SnVO3] (1) were collected at low temperature (110 K; cooling
device from Oxford Instruments) on the powder diffractometer
instrument assembled at the Swiss-Norwegian beam line BM01b at
the European Synchrotron Radiation Facility (ESRF), Grenoble,
France. The beam line receives X-rays from the synchrotron source,
operating with an average energy of 6 GeV and a typical beam
current of 200 mA, from a bending magnet device. The high signal-
to-noise ratio of the data is due to the high brilliance of the
synchrotron beam in combination with a Si (111) crystal multi-
analyzer.
Acknowledgements
This work was developed in the scope of the project (Associate
Laboratory) CICECO-Aveiro Institute of Materials – POCI-01-0145-
˜
ˆ
FEDER-007679 [FCT (Fundac¸ao para a Ciencia e a Tecnologia) ref.
UID/CTM/50011/2013], financed by national funds through the
FCT/MEC and when applicable co-financed by FEDER (Fundo
Europeu de Desenvolvimento Regional) under the PT2020 Partner-
ship Agreement. We wish to thank the European Synchrotron
Radiation Facility (ESRF), Grenoble, France for granting access to
the Swiss-Norwegian beam line BM01b through the approved
project CH-3994. The FCT and the European Union are acknowl-
edged for post-doctoral grants to A.C.G. (SFRH/BPD/108541/2015)
and M.M.A. (SFRH/BPD/89068/2012), co-funded by MCTES and the
European Social Fund through the program POPH of QREN.
˚
The monochromatic wavelength was fixed at 0.504884(8) A and
calibrated against the Si standard NIST 640c [certified cell
˚
parameter a=5.4311946(92) A]. Hard X-rays were selected for data
collection to significantly reduce radiation damage. Even at low
temperature the high brilliance of the synchrotron source led to
visible damage on the samples. To minimize such effects consec-
utive data collections were performed on fresh portions of the
samples by translating the capillaries by ca. 1.3 mm.
A finely powdered sample of 1 was placed inside a Hilgenberg
borosilicate glass capillary with a diameter of ca. 0.6 mm, which
was spun during data collection to improve powder averaging over
the individual crystallites, ultimately removing textural effects (such
as preferred orientation). Data were collected in continuous mode
with accumulation times increasing with the scattering angle. The
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Conflict of Interest
The authors declare no conflict of interest.
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Keywords: vanadates · tin · sodalite topology · epoxidation ·
oxidative dehydrogenation
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Manuscript received: March 22, 2018
Version of record online: &&&, &&&&
ChemCatChem 2018, -53, 1–10
www.chemcatchem.org
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These are not the final page numbers!

Full Papers
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FULL PAPERS
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Let there be sodalite: The coordina-
tion polymer [Et3SnVO3] (1) possesses
a three-dimensional network
Dr. A. C. Gomes, Dr. M. M. Antunes,
Dr. M. Abrantes, Dr. A. A. Valente,
Dr. F. A. A. Paz*, Dr. I. S. Gonc¸alves,
Dr. M. Pillinger*
structure with the sodalite topology,
formed by tetravanadate polyanions,
[V4O12]4ꢀ, that are linked by Et3Sn+
spacers. The catalytic versatility of 1
was demonstrated by applying it for
the epoxidation of olefins, the
oxidative dehydrogenation of
alcohols, and the oxidation of benzyl
alcohol.
1 – 10
An Organotin Vanadate with
Sodalite Topology and Catalytic
Versatility in Oxidative Transforma-
tions
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