Research Article

pubs.acs.org/acscatalysis

Tantalum−Polyhedral Oligosilsesquioxane Complexes as Structural

Models and Functional Catalysts for Epoxidation
Pascal Guillo,†,‡,§ Michael I. Lipschutz,† Meg E. Fasulo,† and T. Don Tilley*,†,‡
†
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States
‡
Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
*
S Supporting Information

ABSTRACT: Tantalum-based supported catalysts have been shown to be very

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selective for epoxidations with aqueous hydrogen peroxide. To gain information

relative to the active site on the surface, access to molecular complexes that
mimic the active site of the catalyst on the surface is of great interest. In this
contribution, several new Ta-polyhedral oligosilsesquioxane (POSS) complexes
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with POSS ligands are used to model silica-bound Ta sites and are shown to be
active as epoxidation catalysts. Notably, a Ta-POSS complex modified by
germanoxy ligands and possessing a dinuclear Ta(μ-O)(μ-OH)Ta core is
observed to be very efficient for the epoxidation of cyclooctene using aqueous
hydrogen peroxide.
KEYWORDS: silsesquioxane, tantalum, catalysis, epoxidation, hydrogen peroxide

■ INTRODUCTION
Single-site, supported catalysts have attracted considerable
attention in the context of probing catalytic mechanisms and
optimizing efficiencies for a wide range of chemical trans-
formations.1−6 Despite tremendous progress in this area,7−9
there remains a markedly incomplete understanding of the
relationship between reaction mechanisms and structural
properties for the active sites of heterogeneous catalysts. One
approach for identifying crucial structural features for supported
catalysts is based on the study of accurate molecular models,
which may be interrogated with a wide array of spectroscopic
methods to establish structure−activity relationships. For this
purpose, polyhedral oligosilsesquioxane (POSS) ligands10−13
and their metal complexes have been extensively employed to
mimic the structure and chemistry of silica-bound metal
species.14−19 Indeed, silsesquioxane compounds can be used
to mimic the different types of silanol groups found on a silica
surface (isolated, vicinal, and geminal) and can provide
information on the role of nearest-neighbor atoms on structure
and reactivity.14 Furthermore, silsesquioxanes may possess pKa
values for Si−OH units that are close to those of silica.20 Thus,
the study of silsesquioxane-based homogeneous models for
single-site heterogeneous catalysts can contribute to a better
understanding of heterogeneous catalysis at the molecular level.
Moreover, they may function as related and efficient
homogeneous catalysts.14
Titanium-POSS (Ti-POSS) complexes, mainly based on the
trisilanol 1 (Scheme 1a), have been extensively studied as
molecular models for silica-supported titanium epoxidation
catalysts such as microporous TS-1 and Ti-MCM-41.21−27
Whereas TS-1 with its hydrophobic pore structure is useful for
the industrial-scale epoxidation of propene with H2O2,28
mesoporous catalysts such as Ti-MCM-41 or Ti-SBA15 have
been developed for higher molecular weight olefins with
alkylhydroperoxides as the oxidant.29−31 However, although
aqueous hydrogen peroxide is a more attractive choice for the
oxidant, due to its low cost and environmental appeal, silica-
supported titanium centers in mesoporous structures are
rapidly degraded under aqueous conditions.30,32,33 Among the
different strategies to improve the catalyst stability, one of the
most promising is the incorporation of the catalytic center into
a hydrophobic environment.32−37 Development of new
materials such as the mesoporous mesophase material Ti-
MMM or the slow addition of H2O2 represent promising
additional approaches for overcoming the problem of catalyst
degradation.38,39 The Ti-POSS homogeneous catalysts are
efficient with alkylhydroperoxides as the oxidant, but only
modest activity is observed in aqueous H2O2.21−25 Only two
reports describe homogeneous Ti-POSS complexes that
efficiently catalyze epoxidation with H2O2 (Scheme 1b).26,27
In these examples involving a Cp*Ti center, it is proposed that
the sterically demanding Cp* ligand stabilizes reactive species
through the catalytic cycle. Immobilization of Ti-POSS
complexes in a hydrophobic environment such as a PDMS
membrane has also been shown to be an effective way to utilize
Ti-POSS complexes for epoxidations with H2O2.40 Also,
organo-bridged silsesquioxane titanates synthesized by a sol−
gel process are efficient catalysts for heterogeneous epoxidation
with hydrogen peroxide.41
Research in this laboratory established the utility of site-
isolated tantalum centers on silica as inherently more selective
than analogous titanium catalysts for epoxidations with aqueous
Received: January 4, 2017
Revised: February 10, 2017
Published: February 14, 2017

© 2017 American Chemical Society 2303 DOI: 10.1021/acscatal.7b00020

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Scheme 1. (a) Trisilanol 1, (b) the Cp’TiCl-POSS Series of Complexes (R = alkyl groups), and (c) Cp*Ta(X)-POSS Complexes
Scheme 2. Ta-SAB15 Catalyst and a Possible Molecular Model
Scheme 3. Syntheses of 6 and 7a
a
(a) Diethyl ether, 23 °C, 6 h. (b) 1, diethyl ether, 23 °C, 15 h.
hydrogen peroxide.33,42−46 This interesting difference in
catalytic behavior points to different catalytic structures and
mechanisms and highlights the need to obtain useful structural
information and molecular models for the tantalum cata-
lysts.33,44 In addition to the Ta-based systems, Nb-based silica
catalysts also exhibit superior performance with hydrogen
peroxide (vs organic peroxides).47−52 In this context, it is
notable that Ta complexes of silsesquioxane ligands, i.e. Ta-
POSS complexes, have received little attention. To the best of
our knowledge, only four reports have described Ta-POSS
complexes, only three of which involve Ta as part of the
silsesquioxane framework.53−56 To gain information and to
improve Ta-based supported catalysts, access to Ta-POSS
complexes is important for the design and development of
more efficient supported catalysts. This laboratory reported the
synthesis and characterization of four Cp*Ta(X)POSS
complexes (X = Cl (2), OTf (3), Me (4), and BArf (5);
Scheme 1c).55 Interestingly, while Notestein and co-workers
reported that silica-supported Cp*Ta is an epoxidation catalyst
with aqueous hydrogen peroxide as oxidant,45 the molecular
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Cp*Ta(X)-POSS complexes (X = Cl (2), OTf (3), Me (4),
BArf (5)) exhibit no activity for this reaction.
The originally reported Ta-SBA15 epoxidation catalysts,
obtained by anchoring the molecular precursor Ta(OiPr)2[OSi-
(OtBu)3]3 onto SBA15 silica, efficiently utilizes aqueous
hydrogen peroxide as the oxidant.42 Importantly, the efficiency
of the H2O2 conversion in this catalysis is significantly
enhanced by the incorporation of hydrophobic substituents
onto the silica surface.43 Although the resulting organic−
inorganic hybrid tantalum catalysts are far superior to
analogous titanium catalysts in promoting selective epoxida-
tions, they are about an order of magnitude lower in catalytic
activity. Thus, an important goal in developing useful supported
tantalum catalysts in selective oxidations is the realization of
higher conversion rates. This might be achieved by chemical
modifications of the catalytic center, and it has been established
that Ti and Ta catalysts exhibit higher activities when M−O−Si
linkages are replaced by M−O−Ge moieties.57−61 Although the
precise origin of this “germanium effect” is yet to be thoroughly
understood, it is of interest to develop structure−activity
relationships for tantalum catalysts with well-defined structures.
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As structural and functional models for supported tantalum
catalysts, Ta-POSS derivatives should prove useful given
identification of catalytically active examples. Currently, no
tantalum-based homogeneous epoxidation catalysts possessing
Ta−O−Ge linkages have been described. In this contribution,
several new Ta-POSS complexes are presented along with their
activities as epoxidation catalysts. Notably, a Ta-POSS complex
modified by germanoxy ligands and possessing a dinuclear
Ta(μ-O)(μ-OH)Ta core is observed to be very efficient for the
epoxidation of cyclooctene using aqueous hydrogen peroxide.
■ RESULTS AND DISCUSSION
Synthesis and Characterization of Ta-POSS Com-
plexes. To mimic the silica-supported Ta catalysts previously
studied (Scheme 2),42 a Ta-POSS complex with −OSi(OtBu)3
ligands was initially targeted. While Ta(OiPr)2[OSi(OtBu)3]3
was used as the Ta precursor in the synthesis of Ta-SBA15
materials, Ta(NMe2)3[OSi(OtBu)3]2 was envisioned as a
particularly useful starting material for incorporating a Ta[OSi-
(OtBu)3]2 group because the condensation of Ta(NMe2)3[OSi-
(OtBu)3]2 with trisilanol 1 was expected to occur with efficient
elimination of 3 equiv of Me2NH and formation of the fully
condensed POSS with Ta in the POSS framework.
The tris(amido) complex Ta(NMe2)3[OSi(OtBu)3]2 (6) was
obtained in 86% yield as a white powder from the reaction
between Ta(NMe2)3Cl2 and 2 equiv of KOSi(OtBu)3 (Scheme
3). Reaction of 6 with trisilanol 1 led to formation of
Ta[OSi(OtBu)3]2-POSS·HNMe2 (7) in 94% yield as a white
powder after precipitation from a diethyl ether solution with
acetonitrile. The X-ray crystal structure of 7 reveals an
octahedral coordination environment at Ta with a molecule
of dimethylamine (Me2NH) as a ligand (Figure 1). This
Figure 1. Molecular structure of 7 displaying thermal ellipsoids at the
50% probability level. H atoms and i-butyl groups were omitted for
clarity.
retention of an equivalent of Me2NH as a ligand has been
observed for other Ta-NMe 2 precursors employed in
protonolysis reactions.62−65 The Ta center in 7 is in a distorted
octahedral environment in which the O atom trans to the amine
ligand is more tightly bound (the Ta−O4 distance is 1.909(6)
Å, whereas other Ta−O distances are 1.939(6)−1.947(6) Å).
The relatively long Ta−N distance of 2.337(6) Å is consistent
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with a dative interaction.62,63 The Ta−OSi(OtBu)3 distances
(1.937 and 1.938 Å) are in the range of those observed for
previously reported Ta(OiPr)2[OSi(OtBu)3]3 (1.860(5) to
2.041(7) Å).42
An accepted mechanistic step for the activation of a
hydroperoxide in a metal-catalyzed epoxidation is protonolysis
of an M−O−Si linkage to produce a (SiOH)M−OOR
intermediate. Indeed, this type of process has been postulated
for Ti-POSS complexes where cleavage of a Ti−O bond (in
preference to Cp−Ti bonding) has been proposed.21,25,66 Thus,
to stabilize the Ta−O bonds toward engagement in this type of
reversible process, a chelating bidentate bis(aryloxide) ligand
was employed. Synthesis of the bidentate ligand LH2 was
adapted from the synthesis of a related compound,67 and
reaction of Ta(NMe2)5 with 1 equiv of LH2 in diethyl ether
afforded Ta(L)(NMe2)3 (8) in 73% yield as a pale yellow
powder (Scheme 4). Subsequent reaction of 8 with 1 equiv of
the trisilanol 1 in toluene led to formation of Ta(L)-POSS·
HNMe2 (9) in 60% isolated yield as a white solid.
The X-ray crystal structures of 8 and 9 (Figure 2) reveal the
presence of a chelating binaphtholate ligand with dihedral
(twist) angles of 50.3 and 52.0°, respectively (Figure 2).
Complex 8 possesses a distorted trigonal bipyramidal geometry,
while in 9, the tantalum center is in an octahedral coordination
environment with a dimethylamine molecule coordinated to
tantalum. As for related Ta compounds with a binaphtholate
ligand, 8 features an oxygen atom from L in an equatorial
position (with Ta−Oeq = 1.937(1) Å), while the other oxygen
is in an axial position with a Ta−Oax distance of 2.052(1) Å.62
To access a molecular precursor with a Ta−O−Ge linkage,
we focused on introduction of −OGeiPr3 ligands, as previously
reported for a Ti−Ge precursor.60 Initial attempts to achieve
this via reaction of Ta(NMe2)3Cl2 with 2 equiv of KOGeiPr3
did not provide the anticipated Ta(NMe2)3(OGeiPr3)2 complex
but instead gave a mixture of products that could not be
separated. The reaction of Ta(NMe2)5 with 5 equiv of
HOGeiPr3 did not give the expected products Ta(OGeiPr3)5
or Ta(NMe2)x(OGeiPr3)5−x but instead provided the ditanta-
lum complex 10 with μ-O and two μ-OH bridges (Scheme 5).
Monitoring the reaction by 1H NMR spectroscopy indicated
clean formation of the initial product Ta(NMe2)(OGeiPr3)4
with 1 equiv of HOGeiPr3 still present in solution. After
removal of solvent under vacuum at room temperature and
redissolution in benzene-d6, a mixture of Ta(NMe2)(OGeiPr3)4
and 10 was observed by 1H NMR spectroscopy. Subsequent
removal of solvent and heating of the resulting solid at 110 °C
under vacuum led to the exclusive and clean formation of
[(iPr3GeO)3Ta]2(μ-OH)2(μ-O) (10) as the sole product. This
transformation is associated with thermal decomposition of
HOGeiPr3 into unidentified volatile products. The synthesis of
10 was accomplished by reaction of Ta(NMe2)5 with 5 equiv of
HOGeiPr3 in pentane, followed by removal of solvent and
heating of the resulting solid at 110 °C under vacuum for 4 h.
Compound 10 was then isolated as a white powder in 85%
yield after precipitation of a solution of 10 into acetonitrile.
Suitable crystals for X-ray crystallography were obtained by
slow evaporation of a solution of 10 in diethyl ether at −30 °C.
The μ-oxo and μ-hydroxo ligands of 10 can be identified by
the X-ray crystallographic data (Figure 3). Thus, two distinctly
shorter Ta−O distances of 2.024(9) and 2.027(10) Å are
attributed to the Ta−O−Ta group, and four longer distances
between 2.113(10) and 2.183(11) Å are assigned to the Ta−
OH−Ta linkages. The Ta−O−Ta bond angle is 6−8° greater
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Scheme 4. Syntheses of 8 and 9a
a
(a) Diethyl ether, 23 °C, 2 h. (b) 1, toluene, 23 °C, 15 h.
Figure 2. Molecular structures of 8 and 9 displaying thermal ellipsoids at the 50% probability level. H atoms and i-butyl groups were omitted for
clarity.
Scheme 5. Synthesis of 10 and 11a
a
(a) Pentane, 23 °C, 3 h, then vacuum, 110 °C, 4 h. (b) 1, diethyl ether, 23 °C, 15 h.
than the Ta−OH−Ta bond angles. This assignment of a Ta(μ-
O)(μ-OH)2Ta core is also consistent with electroneutrality in
the complex, and the presence of the hydroxo groups was
confirmed by infrared spectroscopy, which revealed the
presence of a sharp band at 3647 cm−1 for the O−H stretching
mode. Moreover, on the basis of comparisons to another
dinuclear Ta compound with the same core, [Cp*TaCl2]2(μ-
OH)2(μ-O), 2 bands at 564 and 644 cm−1 were attributed to
Ta−O−Ta vibrations for 10 (vs 577 and 629 cm−1 for
[Cp*TaCl2]2(μ-OH)2(μ-O)).68,69
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Complex 10 appears to represent an interesting precursor to
olefin epoxidation catalysts as it contains Ta−O−Ge linkages as
well as a ditantalum core. The latter feature presents the
opportunity to probe possible cooperative effects between
metal centers in a bimetallic active site, and few detailed studies
on such catalysts have been realized. Previous studies on
supported dititanium catalysts suggest that catalysis by such
species is possible.30,70,71 Additionally, it has been shown that
the catalytically active surface-bound species from the reaction
of Ti(OiPr)4 with silica is an oxo-bridged Ti−O−Ti dimer.70,71
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Figure 3. Molecular structures of 10 and 11 displaying thermal ellipsoids at the 50% probability level. H atoms, i-butyl groups on siloxide ligands,
and i-propyl groups on the germoxy ligands were omitted for clarity.

In related work, a monomeric POSS complex with two Ti Table 1. Cyclooctene Epoxidation Catalyzed by 2−5, 7, 9,
centers linked with an oxo bridge was reported.72 The latter and 11a
complex results from the condensation of CpTiCl3 with
t
Cy6Si6O7(OH)4 to give Cy6Si6O12Ti2Cp2. However, for the catalyst oxidant (h) yieldb(%)
oxidation of cyclohexene with tBuOOH and a catalyst loading TaCp*X-POSS X = Cl (2), Me (3), OTf CHP 24 0
of 2 mol %, the catalytic activity of Cy6Si6O12Ti2Cp2 was much (4), B[C6F5]− (5) TBHP 24 0
lower than that of its analogue with only one Ti center. H2O2, 30% 24 0
Reaction of 10 with 1 equiv of the trisilanol 1 in diethyl ether POSSTa[OSi(OtBu)3]2·HNMe2 (7) CHP 2 24
led to formation of 11, isolated in 95% yield by precipitation TBHP 2 30
from a diethyl ether solution with acetonitrile (Scheme 5). The H2O2, 30% 2 30
crystal structure of 11 revealed that the ditantalum unit is Ta(L)-POSS·HNMe2 (9) CHP 24 0
preserved in the product with μ-oxo and μ-hydroxy bridges, TBHP 24 0
while one of the hydroxyl bridges in 10 is replaced by a siloxide H2O2, 30% 24 0
bridge (Figure 3). The structure of 11 is very unusual for a 11 CHP 22 24
metal-POSS compound in that, to the best of our knowledge, it TBHP
is the first example of a bimetallic complex derived from 1 equiv H2O2, 30% 1 94
of trisilanol 1. As for 10, the Ta centers in 11 are in a highly a
All reactions were performed in toluene at 65 °C with [catalyst] =
distorted octahedral environment with roughly trans-O−Ta−O 0.78 mM and a catalyst:substrate:oxidant of 1:600:50. bYield
angles between 152.3(4) and 170.3(4)°. The presence of the μ- determined by gas chromatography. CHP: cumene hydroperoxide,
OH group is also confirmed by the FTIR spectrum, which TBHP: tert-butyl hydroperoxide.
possesses a characteristic band at 3577 cm−1.
Catalysis. The previously reported TaCp*-POSS complexes
2−555 and the new Ta-POSS compounds 7, 9, and 11 were POSS·HNMe2 (7), a yield of ca. 30% was observed with all
studied as catalysts for epoxidation reactions. The catalytic oxidants. Complex 11, with the germoxy ligands, presented the
efficiencies of these tantalum complexes (2 mol %) in most promising results; a yield of 94% was obtained after only 1
epoxidations of cyclooctene were determined for reactions at h with hydrogen peroxide. A lower conversion (22%) was
65 °C in toluene with various oxidants and an olefin:oxidant observed with CHP as the oxidant (Table 1). Interestingly,
ratio of 12:1 (Table 1). As mentioned in the Introduction, the supported Ta heterogeneous epoxidation catalysts have also
TaCp*X-POSS (X = Cl, Me, OTf, or Barf) complexes 2−5 are shown better results with hydrogen peroxide in comparison to
analogues of titanium-based TiCp*modifiedCl-POSS that have CHP or TBHP.43,44
been reported to be efficient epoxidation catalysts with H2O2 as To further investigate the catalytic behavior of 7 and 11,
the oxidant.26,27 However, attempts to observe catalytic activity additional conditions and substrates were utilized, and the
for 2−5 were unsuccessful, and in all cases, no conversion of results are summarized in Table 2. For 7, an excess of olefin
the cyclooctene was observed after 24 h at 65 °C in toluene. substrate is required for conversion of the alkene into the
Complex 9, with the bidentate bis(aryloxide) ligand, is also corresponding epoxide. When a 1:1 or 1:3 substrate:oxidant
inactive for the epoxidation of cyclooctene with tert-butyl ratio was used, no conversion of the cyclooctene was observed
hydroperoxide (TBHP), cumene hydroperoxide (CHP), and after 24 h at 65 °C. Moreover, even with an excess of alkene,
hydrogen peroxide (H2O2) (Table 1). For Ta[OSi(OtBu)3]2- when no further conversion of alkene was observed by GC, an
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Table 2. Olefin Epoxidation Catalyzed by 7 and 11a

cat/ yieldb (%)
T substrate/ (2nd run,
catalyst substrate (°C) H2O2 t (h) 3rd run) TONc
7 cyclooctene 65 1:600:50 2 30 15
cyclohexene 65 1:600:50 2 22 11
1-octene 65 1:600:50 24 4 2
cyclooctene 65 1:100:100 24 0 0
cyclooctene 65 1:100:300 24 0 0
11 cyclooctene 65 1:100:100 1 31 31
(21, nd)
cyclooctene 65 1:600:50 1 94 47
(79, 76)
cyclooctene 65 1:600:100 1.33 80 80
(63, 50)
cyclooctene 65 1:600:200 23 79 158
cyclooctene RT 1:50:50 24 94 43 Figure 4. Molecular structure of 12 displaying thermal ellipsoids at the
cyclooctene RT 1:100:100 7 67 67 50% probability level. H atoms, i-butyl groups, and [HNMe2]+ were
cyclooctene RT 1:600:50 7 94 46 omitted for clarity.
cyclooctene RT 1:600:100 11 80 80
cyclooctene RT 1:600:200 8 70 139 to have the same 1H NMR spectrum as the one obtained
cyclooctene RT 1:100:200 24 39 39 during the degradation reaction, confirming that 12 is the
cyclohexene RT 1:50:50 23 13 6 product of decomposition and not simply formed during the
cyclohexene RT 1:600:50 7 60 30 crystallization process. Attempts to observe epoxidation of
1-octene RT 1:50:50 23 8 4 cyclooctene with 12 as catalyst showed that there was no
1-octene RT 1:600:50 16 52 26 conversion of the substrate. For this system and in the
a
All reactions were performed in toluene with [catalyst] = 0.78 mM. conditions tested, a labile site on the Ta center seems to be
b
Yield was determined by gas chromatography. cTON: turnover necessary for binding and activation of the oxidant.
number, expressed as mol epoxide/mol catalyst. Of course, the decomposition of 7 to 12 is not possible for a
silica-supported Ta catalyst. However, during the decom-
additional aliquot of 50 equiv of oxidant led to no further position 7, half of the Ta is likely transformed into tantalum
reaction. This behavior strongly suggests that decomposition of oxide after decomplexation from the POSS core. A deactivation
the catalyst occurs during reaction. of the supported catalyst by reaction with water may hinder
To examine the behavior of 7 in the presence of a peroxide formation of the intermediate tantalum−hydroperoxide com-
reagent, this complex was allowed to react in the presence of 3 plex, as occurs with related Ti-based catalysts with aqueous
equiv of H2O2·urea in benzene-d6 at 65 °C (Scheme 6). Note hydrogen peroxide as oxidant.32,33
that this oxidant allows monitoring of the reaction by NMR For 11, with cyclooctene as substrate and a catalyst:alkene:
spectroscopy without the complications associated with a large H2O2 ratio of 1:600:50, the observed conversions were the
excess of water (as in 35% H2O2). This experiment revealed the same at 65 °C or at room temperature (94%), but the reaction
transformation of 7 into a new complex (12), identified by at 65 °C was much faster (1 h vs 7 h at room temperature).
crystallization of the product from the reaction mixture. The When a catalyst:alkene:H2O2 ratio of 1:100:100 was used, the
crystal structure of 12 shows that this complex contains two reaction was more efficient at room temperature (67%
POSS ligands bridged by an octahedral TaO6 center (Figure 4). conversion) than at 65 °C (31% conversion). With an excess
Complex 12 was independently synthesized via reaction of 2 of oxidant (catalyst:alkene:H2O2 ratio of 1:100:200), low
equiv of 1 with 1 equiv of Ta(NMe2)5 (Scheme 6) and shown conversion of cyclooctene was observed (39% at room

Scheme 6. Access to 12 by a Degradation Process of 7 or by Direct Synthesis

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temperature), suggesting a slow decomposition of the catalyst.
This catalyst was efficient even at 0.5% loading, which gave a
70% yield for the epoxidation of cyclooctene. It is also
interesting that at room temperature the catalyst is efficient
with a cyclooctene:H2O2 ratio of 1:1 (94% conversion with a
catalyst:alkene:H2O2 ratio of 1:50:50). Notably, this is in
contrast to Ti-POSS complexes, for which an excess of the
alkene was necessary when alkyl peroxides were used as
oxidants.25 Another interesting feature of 11 is that it is still
efficient after the first run. Indeed, addition of H2O2 after the
conversion of the substrate ceased led to a subsequent
formation of epoxide. This operation was repeated twice. A
loss in conversion was observed after each run, indicating a
potential slow degradation of the catalyst. However, interest-
ingly, with a catalyst:substrate:H2O2 ratio of 1:600:50, no
further loss was observed during the second and third runs. All
of these results might indicate that 11 is not the actual catalyst
but a precatalyst for the epoxidation reaction. Monitoring the
reaction by 1H NMR spectroscopy by addition of 10 equiv of
cyclooctene then 5 equiv of H2O2 (30%) to a solution of 11 in
benzene-d6 and then heating to 65 °C revealed formation of 5
equiv of cyclooctene oxide (100% yield based on H2O2) and
the release of 2 equiv of HOGeiPr3. Attempts to isolate the
resulting compound, which might be the active catalyst, were
unsuccessful.
The reactivity of 11 as a catalyst is strongly influenced by the
solvent. All experiments involved biphasic conditions with the
catalyst and the alkene in toluene and the oxidant in water.
With THF as the solvent, in which both aqueous hydrogen
peroxide and 11 are soluble, no conversion of cyclooctene was
observed. This suggests that 11 is decomposed in the presence
of an excess of oxidant and that this decomposition is
diminished under biphasic conditions in which the catalyst is
exposed to a low concentration of oxidant. However, as
observed with the lower yield after the first run, a slow
decomposition process seems to occur. For cyclohexene and 1-
octene as substrate, lower conversions were observed even with
an excess of the substrate. However, only the epoxide was
detected, and no enone, enol, or diol products were detected by
GC.
The fact that 11 is an efficient catalyst for epoxidations while
7 rapidly decomposes under the same conditions provides
information that may be utilized for the design of more efficient
Ta-based catalysts. First of all, Ta compound 12 is more stable
toward oxidizing conditions than the monometallic compound
7. Also, the Ta2O2 core of 11 with the μ-oxo/hydroxo bridges is
reminiscent of a structural feature for the active site of
hydroxylase methane monooxygenase (MMO), which pos-
sesses 2 Fe(III) centers with μ-hydroxo bridges in the resting
state of the catalytic cycle and a di(μ-oxo)diiron(IV) Fe2O2
“diamond core” structure responsible for oxidation of methane
to methanol.73−77 However, in the case of 11, the bridging
oxygen atom is apparently not transferred to the substrate, as
indicated by the absence of reaction between 11 and
cyclooctene in benzene-d6 at 65 °C for 4 h in the absence of
oxidant. Moreover, 2 equiv of HOGeiPr3 is released when H2O2
is added, suggesting that oxidizing species are formed on the Ta
center(s) by exchange of two germanoxy ligands by (hydro)-
peroxo ligand(s). As in MMO enzymes, the presence of the oxo
bridge probably stabilizes the oxidizing species and prevents
rapid decomposition of the catalyst. As mentioned in the
Introduction, the presence of germanium has been described in
the literature to enhance the catalytic activity of catalysts. In the
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absence of a catalyst possessing the same Ta2O2 core and no
germanoxy ligands, the influence of the germanium is difficult
to evaluate for 11. However, as previously mentioned, only 2
equiv of germanol is released during the catalytic cycle,
suggesting that 2 germanoxy ligands are still coordinated to the
Ta centers during the catalysis.
In conclusion, four new Ta-POSS complexes were
synthesized, characterized, and examined as catalysts for
epoxidation reactions. In the context of development of new
homogeneous and supported oxidation catalysts based on Ta, 7
and 11 are most interesting. Indeed, 7, with one Ta center and
two −OSi(OtBu)3 ligands, decomposes after a few catalytic
cycles into inactive 12, possessing two POSS ligands. The
decomposition of 7 into 12 suggests that the Ta center can be
extracted from the POSS ligand, and a similar process might be
possible on the silica surface, leading to deactivation of a
supported catalyst. To the best of our knowledge, 11 is the first
Ta-POSS complex that possesses catalytic epoxidation activity
and is an efficient catalyst for the epoxidation of cyclooctene
using aqueous hydrogen peroxide. Moreover, only a small loss
of activity is observed even after three runs of catalysis. The
presence of μ-oxo and μ-hydroxo bridges, and perhaps the
germanoxy ligands, are possible keys for stabilization of Ta
during the catalysis.
■ EXPERIMENTAL SECTION
General Considerations. All manipulations of air sensitive
compounds were conducted under a nitrogen atmosphere using
standard Schlenk techniques or a nitrogen atmosphere glovebox.
Solvents were stored in PTFE-valved flasks after drying using solvent
purification systems or by distillation under nitrogen from appropriate
drying agents. Benzene-d6 was purchased from Cambridge Isotope
Laboratories, dried over Na/K alloy, and then degassed by several
freeze−pump−thaw cycles. NMR spectra were recorded on Bruker
spectrometers at room temperature unless otherwise noted. Spectra
were referenced internally by solvent peaks for 1H and 13C{1H} NMR
and tetramethylsilane for 29Si−1H HMBC experiments. X-ray analyses
were carried out at the UC Berkeley CHEXRAY crystallographic
facility. Measurements of 7, 8, 9, 10, 11, and 12 were made on an
APEX CCD area detector with Mo Kα radiation (λ = 0.71069 Å)
monochromated with QUAZAR multilayer mirrors. Elemental
analyses were performed by the College of Chemistry Microanalytical
Laboratory at the University of California, Berkeley. Infrared spectra
were collected using a Thermo Nicolet 6700 FTIR spectrometer. GC
analyses were performed on an HP 6890N system using a
phenylmethyl polysiloxane DB-5 capillary column (30.0 m × 320
μm × 1.00 μm), and integration was performed relative to a dodecane
internal standard. No diols were detected in the reaction mixtures by
GC analyses. HOSi(OtBu)3,78 KOSi(OtBu)3,78 Ta(NMe2)3Cl2,79
HOGeiPr3,60 and 2−555 were prepared according to literature
methods. Incompletely condensed silsesquioxane 1 was purchased
from Hybrid Plastics Inc. and dried overnight under vacuum at 50 °C
prior to use. Ta(NMe2)5 was purchased from Strem Chemicals, Inc.
and freshly sublimed prior to use. Cyclohexene and 1-octene were
purchased from Aldrich and dried over CaH2 prior to use. tert-Butyl
hydroperoxide (TBHP, 5.5 M in decane), cumene hydroperoxide
(CHP, 80%, technical grade), hydrogen peroxide (H2O2, 30 wt % in
H2O), urea hydrogen peroxide, 2-tert-butyl-4-methylphenol, and
cyclooctene were purchased from Aldrich and used as received. All
other chemicals were purchased from commercial sources and used
without further purification.
Ta(NMe2)3[OSi(OtBu)3]2 (6). To 518 mg (1.35 mmol) of a
suspension of Ta(NMe2)3Cl2 in 5 mL of diethyl ether was added
KOSi(OtBu)3 (816 mg, 2.7 mmol) in 5 mL of diethyl ether. The
mixture was stirred at room temperature for 6 h. The solution turned
yellow, and a white precipitate of KCl appeared. The suspension was
filtered on a pad of Celite, and the pale yellow filtrate was concentrated
DOI: 10.1021/acscatal.7b00020
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ACS Catalysis
to about 1 mL and stored at −30 °C for crystallization. After 24 h,
crystals of 6 were isolated by filtration and dried under vacuum to give
980 mg (86%) of the product as a white solid. This compound is not
stable at room temperature and had to be stored at −30 °C under
nitrogen atmosphere.1H NMR (C6D6, 600 MHz, 25 °C): δ 3.56 (s,
18H), 1.46 (s, 54H). 13C{1H} NMR (C6D6, 600 MHz, 25 °C) δ 72.7,
47.5, 32.2. 29Si{1H} NMR (C6D6, 600 MHz, 25 °C) δ −98.10. Anal.
Calcd for C30H72N3O8Si2Ta: C, 42.89; H, 8.64; N, 5.00. Found: C,
42.58; H, 8.73; N, 4.73.
Ta[OSi(OtBu)3]2-POSS·HNMe2 (7). To 500 mg (0.63 mmol) of
the trisilanol 1 in 5 mL of diethyl ether was added a solution of 6 (530
mg, 0.63 mmol) in 5 mL of diethyl ether. The resulting solution was
stirred at room temperature for 15 h. After filtration of a small
precipitate on a short pad of Celite, the solution was evaporated under
reduced pressure. The residue was dissolved in 2 mL of diethyl ether,
and acetonitrile was then added dropwise to the pale yellow solution
to precipitate 7. This mixture was kept at −30 °C for 12 h to achieve
complete precipitation. 7 was isolated by filtration and dried under
vacuum to give 820 mg (84%) of the product as a white powder.
Crystals suitable for X-ray diffraction were obtained by cooling a
saturated solution of 7 in pentane at −30 °C. 1H NMR (C6D6, 600
MHz, 25 °C) δ 4.37 (quin, 1H, 5.4 Hz), 2.75 (d, 6H, 5.4 Hz), 2.16 (m,
7H), 1.53 (s, 54H), 1.10−1.27 (m, 42H), 0.90−0.95 (m, 6H), 0.84
(dd, 6H, 16.6 Hz, 6.6 Hz), 0.71 (dd, 2H, 15 Hz, 7.8 Hz). 13C{1H}
NMR (C6D6, 600 MHz, 25 °C) δ 73.35, 41.69, 32.60, 25.44, 25.20,
24.96, 24.93, 24.61, 24.32, 23.97, 23.90, 23.56. 29Si{1H} NMR (C6D6,
600 MHz, 25 °C) δ −98.4, −68.9, −67.8, −65.9, −64.8. Anal. Calcd
for C54H124NO20Si9Ta: C, 42.08; H, 8.11; N, 0.91. Found: C, 41.83; H,
8.07; N, 1.15.
LH2 (Adapted from Ref 67). 2-tert-Butyl-4-methylphenol (3.73 g,
22.7 mmol) was dissolved in 23 mL of glacial acetic acid. Concentrated
sulfuric acid (4.5 mL) was added to a solution of K2Cr2O7 (2.27 g,
7.72 mmol) in 24 mL of water. This solution was added dropwise to
the solution of the phenol over 30 min at 50 °C. The orange solution
turned green, and an orange oil appeared. The solution was stirred at
50 °C for 3 h. After cooling to room temperature, 100 mL of water
was added, and the aqueous phase was extracted with 200 mL of
dichloromethane. The operation was repeated two more times (until
the organic phase was colorless). After evaporation of the organic
phase, the orange oil remaining was purified by column chromatog-
raphy (eluant: hexane:diethyl ether = 99:1) and after concentration
gave 1.2 g (33%) of the product as a white foam. 1H NMR (C6D6, 600
MHz, 25 °C) δ 7.18 (s, 2H), 6.73 (s, 2H), 5.12 (s, 2H, OH), 2.11 (s,
6H, Me), 1.52 (s, 18H, tBu). 13C{1H} NMR (C6D6, 600 MHz, 25 °C)
δ 150.75, 130.19, 129.66, 129.10, 123.62, 35.50, 30.24, 21.17. Anal.
Calcd for C22H30O2: C, 80.94; H, 9.26. Found: C, 80.65; H, 9.11.
Ta(L)(NMe2)3 (8). To a solution of LH2 (200 mg, 0.61 mmol) in 5
mL of diethyl ether was added a solution of Ta(NMe2)5 (246 mg, 0.61
mmol) in 5 mL of diethyl ether via canula transfer. After stirring at
room temperature for 2 h, the resulting yellow/orange solution was
concentrated under vacuum. The light orange solid was washed with 5
mL of cold diethyl ether and gave 284 mg (73%) of the product as a
pale yellow solid. Crystals of 8 suitable for X-ray analysis were
obtained by slow diffusion of pentane into a solution of 8 in toluene at
−30 °C. 1H NMR (C6D6, 600 MHz, 25 °C) δ 7.25 (s, 2H), 7.11 (s,
2H), 3.18 (s, 18H, NMe2), 2.30 (s, 6H, Me), 1.54 (s, 18H, tBu).
13
C{1H} NMR (C6D6, 600 MHz, 25 °C) δ 159.07, 132.72, 131.97,
128.85, 126.75, 45.81, 35.50, 30.94, 21.47. Anal. Calcd for
C28H46N3O2Ta: C, 52.74; H, 7.27; N, 6.59. Found: C, 52.98; H,
7.14; N, 6.52.
Ta(L)-POSS·HNMe2 (9). Toluene (10 mL) was added to a solid
mixture of 8 (100 mg, 0.16 mmol) and 1 (118 mg, 0.15 mmol). After
stirring at room temperature for 15 h, the resulting pale yellow
solution was evaporated under vacuum. The resulting foam was
dissolved in 1 mL of diethyl ether, and 5 mL of hexamethyldisiloxane
was added. After 24 h at −30 °C, a white precipitate was isolated by
filtration and dried under vacuum to give 129 mg (60%) of the
product as a white foam. Crystals suitable for X-ray diffraction were
obtained by cooling a saturated solution of 9 in pentane at −30 °C. 1H
NMR (C6D6, 600 MHz, 25 °C) δ 7.28 (s, 2H), 6.99 (s, 2H), 2.27 (s,
2310
Research Article
6H), 2.26 (s, 6H), 2.22−2.10 (m, 7H), 1.70 (s, 18H), 1.62 (sept, 1H,
6.6 Hz), 1.21 (d, 6H, 6.6 Hz), 1.18 (d, 6H, 6.6 Hz), 1.13 (d, 12H, 6.6
Hz), 1.11 (m, 12H), 1.06−1.02 (m, 2H), 0.93−0.84 (m, 16H), 0.55
(d, 2H, 7.2 Hz). 13C{1H} NMR (C6D6, 600 MHz, 25 °C) δ 156.30,
138.56, 133.43, 131.85, 129.87, 127.48, 42.01, 35.59, 26.91, 26.62,
26.43, 26.42, 26.28, 26.20, 26.13, 25.22, 25.04, 24.98, 24.90, 24.87,
24.37, 23.72, 23.59, 23.48, 23.42, 21.26. 29Si{1H} NMR (C6D6, 600
MHz, 25 °C) δ −62.10, −65.38, −67.57, −68.73. Anal. Calcd for
C52H98NO14Si7Ta: C, 46.65; H, 7.38; N, 1.05. Found: C, 46.28; H,
7.44; N, 0.91.
[(iPr3GeO)3Ta]2(μ-OH)2(μ-O) (10). To a solution of Ta(NMe2)5
(0.500 g, 1.25 mmol) in 20 mL of pentane was added HOGeiPr3 (1.36
g, 6.23 mmol) in 20 mL of pentane via canula transfer. After stirring at
room temperature for 3 h, the resulting pale yellow solution was
evaporated under vacuum at room temperature and then at 110 °C for
4 h. The resulting white solid was then dissolved in 2 mL of diethyl
ether, and acetonitrile was added dropwise to precipitate 10. After 24 h
at −30 °C to achieve precipitation, a white precipitate was isolated by
filtration and dried under vacuum to give 2.15 g (85%) of the product
as a white powder. Crystals suitable for X-ray diffraction were obtained
by cooling a saturated solution of 10 in diethyl ether at −30 °C. 1H
NMR (C6D6, 600 MHz, 25 °C) δ 1.73 (sept, 18H, 7.8 Hz), 1.40 (d,
108H, 7.8 Hz). 13C{1H} NMR (C6D6, 600 MHz, 25 °C) δ 20.32,
19.43. Anal. Calcd for C54H128Ge6O9Ta2: C, 37.72; H, 7.50. Found: C,
38.07; H, 7.28.
[(iPr3GeO)2Ta]2(μ-OH)(μ-O)(μ-OSi)-POSS·HNMe2 (11). To 0.500
g (0.63 mmol) of the trisilanol 1 in 5 mL of diethyl ether was added a
solution of 10 (1.09 g, 0.63 mmol) in 5 mL of diethyl ether. The
resulting solution was stirred at room temperature for 15 h. After
filtration of a small precipitate on a short pad of Celite, the solution
was evaporated under reduced pressure. The residue was dissolved in 1
mL of diethyl ether, and acetonitrile was then added dropwise to the
pale yellow solution to precipitate 11. This mixture was kept at −30
°C. After 12 h, a white precipitate was isolated by filtration and dried
under vacuum to give 1.23 g (95%) of the product as a white powder.
Crystals suitable for X-ray diffraction were obtained by cooling a
saturated solution of 11 in diethyl ether at −30 °C. 1H NMR (C6D6,
600 MHz, 25 °C) δ 4.52 (s, 1H), 2.11−2.26 (m, 7H), 1.75−1.83 (m,
12H), 1.36−1.43 (m, 78H), 1.18−1.24 (m, 30H), 1.12 (d, 6H, 6.6
Hz), 0.86−0.98 (m, 14H). 13C{1H} NMR (C6D6, 600 MHz, 25 °C) δ
26.90, 26.81, 26.76, 26.67, 26.61, 26.51, 26.30, 25.63, 25.34, 25.19,
25.02, 24.96, 24.64, 24.37, 24.13, 23.49, 20.48, 20.21, 20.15, 20.00,
19.98, 19.94, 19.63. 29Si{1H} NMR (C6D6, 600 MHz, 25 °C) δ
−69.91, −67.59, −65.81, −62.14. Anal. Calcd for
C64H148Ge14O18Si7Ta2: C, 37.41; H, 7.26. Found: C, 37.44; H, 7.28.
[Ta-(POSS)2][H2NMe2] (12). To 200 mg (0.25 mmol) of the
trisilanol 1 in 5 mL of diethyl ether was added a solution of
Ta(NMe2)5 (51 mg, 0.13 mmol) in 5 mL of diethyl ether. The
resulting solution was stirred at room temperature for 12 h. After
filtration of a small precipitate on a short pad of Celite, the solution
was evaporated under reduced pressure. The residue was dissolved in 1
mL of diethyl ether, and acetonitrile was then added dropwise to the
pale yellow solution to precipitate 12. This mixture was kept at −30
°C. After 12 h, a white precipitate was isolated by filtration and dried
under vacuum to give 150 mg (65%) of the product as a white powder.
Crystals suitable for X-ray diffraction were obtained by slow
evaporation of a saturated solution of 12 in benzene at room
temperature. 1H NMR (C6D6, 600 MHz, 25 °C) δ 8.49 (s, 2H), 2.11−
2.26 (m, 14H), 2.05 (s, 6H), 1.25 (d, 36H, 6.6 Hz), 1.16 (d, 36H, 6.6
Hz), 1.12 (d, 12H, 6.6 Hz), 0.87 (m, 16H), 0.81 (d, 12H, 7.2 Hz).
13
C{1H} NMR (C6D6, 600 MHz, 25 °C) δ 35.28, 26.94, 26.54, 26.35,
25.13, 24.93, 24.90, 24.04, 23.63. 29Si{1H} NMR (C6D6, 600 MHz, 25
°C) δ −67.87, −64.46, −65.00. Anal. Calcd for C58H134NO24Si14Ta: C,
38.62; H, 7.48; N, 0.78. Found: C, 38.38; H, 7.38; N, 0.75.
Catalytic Alkene Epoxidation. Under a flow of nitrogen, to a
0.78 mM solution of the complex in 5 mL of toluene in a 25 mL three-
necked round-bottom flask fitted with a reflux condenser and two
septums were added the alkene and dodecane (68 μL) as an internal
standard. The vessel was immersed in an oil bath where it was allowed
to equilibrate for 15 min at the desired temperature. The oxidant was
DOI: 10.1021/acscatal.7b00020
ACS Catal. 2017, 7, 2303−2312
ACS Catalysis
added via syringe to the rapidly stirred solution to access the targeted
catalyst:alkene:oxidant ratio. The course of the reaction was monitored
by GC by taking aliquots in the organic phase, and products were
assigned based on known samples analyzed under the same conditions.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b00020.
Crystal data for compounds 7, 8, 9, 10, 11, and 12; CIF
files can also be obtained free of charge from the
Cambridge Crystallographic Data Centre under reference
numbers 1525464, 1525465, 1525466, 1525467,
1525468, and 1525469 (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: tdtilley@berkeley.edu.
ORCID
Pascal Guillo: 0000-0002-9818-7824
Present Address
§ 1997, 2411−2412.
P.G.: Univ Toulouse, UPS, INPT, CNRS, LCC, 205 Route
Narbonne, F-31077 Toulouse, France. Univ Toulouse, Inst
Univ Technol Paul Sabatier, Dept Chim, Ave Georges
Pompidou, BP 20258, F-81104 Castres, France.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was primarily funded by the U.S. Department of
Energy, Office of Science, Office of Basic Energy Sciences,
Chemical Sciences, Geosciences, and Biosciences Division
under Contract DE-AC02-05CH11231.
■
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2312 DOI: 10.1021/acscatal.7b00020

ACS Catal. 2017, 7, 2303−2312