Académique Documents
Professionnel Documents
Culture Documents
pubs.acs.org/CR
Surface Organometallic and Coordination Chemistry toward SingleSite Heterogeneous Catalysts: Strategies, Methods, Structures, and
Activities
Christophe Coperet,*, Aleix Comas-Vives, Matthew P. Conley, Deven P. Estes, Alexey Fedorov,
Victor Mougel, Haruki Nagae,, Francisco Nunez-Zarur, and Pavel A. Zhizhko,
Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir Prelog Weg 15, CH-8093 Zurich, Switzerland
Department of Chemistry, Graduate School of Engineering Science, Osaka University, CREST, Toyonaka, Osaka 560-8531, Japan
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28, 119991 Moscow, Russia
S Supporting Information
*
CONTENTS
1. Introduction
2. Concepts, Denitions, Tools, and Practical Considerations
2.1. Concepts and Denitions
2.2. Toolbox of Characterization Methods
2.3. Practical Aspects
2.3.1. Preparation and Characterization of the
Supports (Calcination, Dehydroxylation,
and Passivation)
2.3.2. Grafting
2.3.3. Storage and Handling
3. Description of the Surface Chemistry on Oxides
3.1. General Concepts, Strategy, and Methods
3.2. Structure of Surface Species Resulting from
Grafting of the Molecular Precursors
3.2.1. Silica-Supported Well-Dened Metal
Sites
3.2.2. Alumina-Supported Metal Complexes
3.2.3. SilicaAlumina Supported Metal Complexes
3.2.4. Other Supports
3.3. Evolution of Well-Dened Surface Sites
upon Post-Treatment and/or Functionalization
3.3.1. Calcination
3.3.2. Thermolysis under Vacuum or Inert Gas
3.3.3. Thermal Treatment under H2
3.3.4. Thermal Treatment under H2S
XXXX American Chemical Society
B
C
C
C
E
E
E
G
G
G
G
G
AP
AS
AV
AZ
AZ
BA
BB
BC
BC
BC
BC
BC
BC
BD
BD
BD
BE
BE
BF
BF
BH
BH
BH
BI
BI
BI
BJ
BJ
BJ
BK
BM
BM
BM
BM
BO
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
4.7.3. Cross-Metathesis of Methane and Higher Alkanes
4.7.4. Nonoxidative Methane Coupling
4.8. Dehydrogenation of Alkanes
4.9. Epoxidation of Alkenes
4.10. Oxidation and Deperoxidation of Alkanes
4.11. Other Selected Catalytic Transformations
4.11.1. Hydroamination
4.11.2. Hydrosilylation
4.11.3. Other Reactions
5. Emerging Fields
5.1. Well-Dened Catalysts through Grafting on
Advanced Functional Materials
5.2. Molecular Approach Beyond Well-Dened
Heterogeneous Catalysts
6. Conclusions
Associated Content
Supporting Information
Author Information
Corresponding Author
Notes
Biographies
Acknowledgments
Dedication
Abbreviation List
References
Review
BP
BP
BQ
BQ
BT
BU
BU
BU
BV
BV
BV
BW
BX
BY
BY
BY
BY
BY
BY
CA
CA
CA
CB
1. INTRODUCTION
The chemical industry relies on catalytic processes, which
involve mainly heterogeneous catalysts because they oer many
advantages over their homogeneous counterparts such as easier
separation of catalysts from reaction products, their applicability
to continuous ow processes, and their recyclability (often by
simply heating in the presence of air or H2).1,2 However,
homogeneous catalysts display several advantages over
heterogeneous catalysts. For example, homogeneous catalysts
are often active at lower temperatures, have higher selectivities,
and are chemically better dened; all active sites have ideally a
known and uniform structure. In particular, the well-dened
nature of their active sites, or at least of the precatalyst
structures, allows for more rational catalyst development
through structureactivity relationships.
Heterogeneous catalysts are usually prepared via the
dispersion of a metal salt/precursor onto a support. These
materials are typically heated under a gas stream, e.g., air, H2, ...,
giving dispersed metal ions with a variable number of MO
bonds between the support and the metal sites or supported
metal particles. Such catalysts contain a broad distribution of
metal coordination environments, and often only a small
fraction of those are active in catalysis. These properties make
characterization at the molecular level dicult, if not
impossible, thereby preventing rational catalyst development.
Thus, the active sites of many heterogeneous catalysts are
matters of intense debate, e.g., the Phillips ethylene polymerization catalyst, ZieglerNatta olen polymerization catalyst,
Caton propane dehydrogenation catalyst, tungsten oxide and
rhenium oxide olen metathesis catalysts, propylene epoxidation catalyst, and vanadyl catalyst for oxidative propane
dehydrogenation, to name but a few.39
To combine the advantages of both homogeneous and
heterogeneous catalysis, research eorts have been directed
toward the generation of heterogeneous catalysts with wellB
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 1. Dehydroxylation of a metal oxide surface and grafting LnMXx onto MSOH
Raman spectroscopy
UVvis
XPS, Auger spectroscopy
Mossbauer spectroscopy
XANES
EXAFS
EPR
solid-state NMR
refs
1
1
39,4352
6,45,47,52,53
5258
1
1
1,59,60
1,59,60
1,58
6176
7782
8385
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 1. (a) Compacting and sieving the support. (b) Calcination of the support in static (left) or ow conditions (right). (c) Rehydroxylation of
the support. (d) Dehydroxylation of the support (for Tdehydroxylation > 500 C quartz reactors are necessary). (e) Titration of surface hydroxyls using
MeMgBr solution in Et2O and GC quantication of released methane.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Specic glassware and procedures based on Schlenk and highvacuum techniques have been developed throughout the years
to allow for easy and reproducible syntheses. These procedures
require high vacuum (105 mbar), heating, and pristine storage
capabilities. We will present an overview of relevant
experimental setups and processes.
2.3.1. Preparation and Characterization of the
Supports (Calcination, Dehydroxylation, and Passivation). Supports used in SOMC can be prepared and
characterized using similar procedures. It is important to
evaluate the structure of the support after each step of the
preparation process because some oxides can readily change
phase or sinter in the presence of water when heated. Oxides
are typically purchased or prepared by solgel or alternative
methods as ne powders. A trick of the trade is to agglomerate
the ne powder into larger, easier to lter, particles by wetting
with water followed by slow evaporation at 120 C in an oven
solely used for inorganic solids. For silica and alumina, the
typical compaction steps are summarized in Figure 1a. A slurry
of the oxide powder in distilled water is dried at ca. 120 C for
several days in an oven, resulting in the formation of large
agglomerates. These agglomerates are sieved to select particles
of 250400 m in size. This treatment does not change the size
E
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 2. (a) Grafting in a Schlenk ask. (b) Grafting in a double-Schlenk ask. (c) Grafting by sublimation of the precursor using break-seal
technique.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 4. (a) Types of silanols. (b) Infrared spectra of Aerosil-200 partially dehydroxylated at 200 and 700 C (SiO2200 and SiO2700). (c) Siloxane
rings. (d) Eect of temperature on surface OH density.
ranging from exible 12-membered rings to strained 4membered rings (Figure 4). The silica surface exposes siloxane
rings/bridges and is also terminated with dierent types of
silanols (Figure 4a). Geminal and isolated silanols are present
even at very high thermal treatment temperatures (>700 C)
and are readily observable using IR spectroscopy.34,106 Vicinal
silanols are two silanol sites in close proximity on the surface
that form hydrogen bonds with one another.40,42 Vicinal
silanols appear in the IR spectrum as a broad red-shifted band
centered at 3650 cm1. Treating silica at temperatures above
150 C under vacuum or in a stream of (inert) gas results in
desorption of physisorbed water. Above this temperature vicinal
silanols begin to condense to form siloxane bridges liberating
more water. Using fumed Aerosil-200 (200 m2 g1) as an
example, the decrease of surface silanol concentration is nearly
exponential with increasing temperature (Figure 4d). The
SiOH density decreases from ca. 3 OH nm2 to ca. 0.8 OH
nm2 for Aerosil-200 partially dehydroxylated at 200 and 700
C. In silica partially dehydroxylated at 700 C (SiO2700)
mostly isolated silanols are present, but 510% of the silanols
are also geminal.70 As the dehydroxylation temperature
increases more, strained siloxane bridges, such as 4-membered
ring siloxanes, are formed.
Cluster and periodic models of the silica surface have been
reported.107 The cluster approach has been used extensively to
model isolated geminal and vicinal silanols, and the reactivity of
these sites with organometallic complexes. Siloxane cages with
dierent SiO rings sizes are of common use in the modeling
of silica surfaces. Figure 5a shows typical siloxane cages used in
the modeling of isolated silanols, whereas Figure 5b shows a
typical model for a geminal silanol.
Several periodic models have been also proposed for the
silica surface. A periodic silica surface containing 26 SiO2 units
was cleaved from an amorphous silica bulk structure108 and
terminated with OH group,109 the nal surface containing 5.8
Figure 5. (a) Typical cluster models of SiO2 for isolated silanols with
dierent ring cages and (b) cluster model of a geminal silanol. (c) Top
and side views of the amorphous model with OH coverage equal to 1.5
OH nm2 from ref 110. (d) A crystalline models based on the (111)
surface of -cristoballite with OH coverage equal to 1.4 OH nm2
from ref 112.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AA
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AB
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AC
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AD
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AE
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AF
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AG
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AH
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AI
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
AJ
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 2. continued
Estimated value.
AK
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 4. (a) Grafting of Bis(trimethyl)silylamide Complexes on Silica and (b) Possible Surface Species with Lanthanide and
Group 3 (Ln) Metal Complexes
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Metal Cyclopentadienyl Complexes. Grafting cyclopentadienyl complexes, CpyM(X)xLn (Cp = C5H5 or C5Me5) on
partially dehydroxylated silica leads to protonolysis of the X
ligand. These results are summarized in Table 2i. Note that for
homoleptic M(Cp)n complexes grafting on silica forms (
SiO)M(Cp)x1 with the release of CpH (Table 2i, entries 3, 4,
8, 9).
Metal Aluminate Complexes. The reaction of lanthanide
amides with AlMe3 species forms Ln(AlR4)3 complexes.229236
These complexes react with partially dehydroxylated silica to
give a mixture of surface species. In general, Ln(AlR4)3 is
proposed to react with silica to form mono- and bis-grafted
lanthanide species and alkylaluminum grafted species shown in
Scheme 8.237,238 Grafting of some other aluminate-supported
lanthanide derivatives was also studied and shows similar results
(Table 2j).
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 6. (a) IR spectra of -Al2O3 treated at dierent temperatures. (b) Assignment of the peaks observed in the IR. (c) OH density (in OH nm2)
and surface area (in m2 g1) as a function of temperature.
mobility increases, leading to a faster phase transition to /alumina. The presence of H2O (steam) above 700 C facilitates
the phase transition.355
Mesostructured -alumina can be prepared by solgel
process in the presence of structure directing agents and has
surface area ranging from 600800 m2 g1 and 2 nm pore
size.356358 Alumina obtained by ame pyrolysis of AlCl3, H2,
and O2, such as Aeroxide Alu C from Evonik, is a mixture of
and phases that have a lower surface area of around 120 m2
g1. Alu C is more stable and more IR transparent than pure alumina, which can be helpful to monitor the evolution of
surface sites, in particular because - and -alumina share
similar bulk and surface properties.
The presence of two types of Al-sites in the bulk reects on
the rich surface chemistry of -alumina surfaces. Surface
aluminum sites can be hexa- (AlVI), penta- (AlV), tetra(AlIV), and tricoordinate (AlIII). The surface also contains
terminal AlOH group bound to AlIV, AlV, and AlIV as well as
2- or 3-OH bridging between Al sites. The OH vibration
bands and the corresponding sites are summarized in Figure
6a,b, and beneath each structure is the OH of each AlOH.
These diverse surface functionalities give rise to a complex IR
spectrum of -alumina in the OH region (Figure 6a) and result
in a dierence of reactivity between each type of OH and Al
site. Similar to silica, applying a thermal treatment to alumina
under vacuum or inert gases leads to a decrease in the OH
intensity, indicating that the AlOH density decreases (Figure
6c). For example, Al2O3500 and Al2O3700 have an OH density
of 2.0 and 0.7 OH nm2, and fully dehydroxylated alumina can
be obtained at ca. 1000 C (Figure 6c). However, at 700800
C -alumina transitions to and phases according to powder
XRD diraction. This transition is also accompanied by a slight
loss of surface area (Figure 6c).
In contrast to silica, the overall shapes of the OH bands in IR
are not dramatically aected as a function of temperature,
indicating that the dierent AlOH sites in Figure 6b are
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
AT
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 3. continued
Degussa Aeroxide AluC (100 m2 g1). bJohnson Matthey -Boehmite monohydrate (200 m2 g1). cAmerican Cyanamid, PHF (150 m2 g1).
SASOL SBa
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Sites (a) are solely observed at low rhenium loading; both (a) and
(b) present at higher loading.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
AW
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Table 4. continued
a
Akzo-Nobel (HA-S-HPV, Si/Al 75/25, 480 m2 g1). bKetjen (Si/Al 75/25, 375 m2 g1). cEstimated value. dStructure proposed based on analogy to
other surface species.
reactivity of partially dehydroxylated magnesia toward Rh(allyl)3, studied by IR spectroscopy and quantication of gases
evolved, was found to be much lower compared to silica,
alumina, and titania.126 This is in line with lower pKa values of
surface MgOH groups. Thus, similarly to what is observed for
silica, late metal alkyls display low reactivity toward surface
hydroxyls and complexes bearing anionic O-ligands are
preferred for grafting. More recently a series of well-dened
magnesia-supported Rh, Ir, and Au complexes was reported
(Table 5). Grafting of metal acetylacetonates leads to
elimination of acac ligand and formation of isolated
monografted surface species. In all cases interaction with an
additional surface oxygen atom was evidenced by EXAFS.
Although released Hacac reacts with magnesia and remains at
the surface, and thus cannot be quantied, changes in IR
vibrations and bond distances given by EXAFS conrm
grafting. In contrast to single-site late transition metals on
other supports, Rh and Ir magnesia-supported species stay welldispersed under H2 and CO, leading to bis-carbonyl species in
the latter conditions.
3.2.4.2. Titania TiO2. TiO2-anatase crystals are dominated
by (101) surfaces as a major facet, the (001) being a minor
one.423 The highest frequency in the IR of TiO2-anatase was
assigned to TiV-1OH groups located on the (001) surface,
whereas the lowest one was assigned to TiVIOH2 located on
the (101) surface.
AX
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Nominal value.
AY
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 13. Cp*ZrMe2+ complex on the (a) SA-SB and (b) SB sites. (c) Insertion of benzene into the ZrO bonds of the grafted Cp*ZrMe2+ species
and displacement from the SA and SB sites.
Scheme 29. Evolution of Surface Species upon Thermolysis under Oxygen-Free Conditions
BA
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 30. (a) Hydrogenolysis of Supported Alkyl Complexes and (b) Surface Hydrides of Group 46 Metals on Various
Supports
Table 6. Early Transition-Metal Hydrides (Group 46) and Their Characteristic IR Signatures
compound
name
MH (cm1)
refs
(SiO)3TiH
(Si/AlO)3TiH
(SiO)3ZrH
(SiO)2ZrH2
(Si/AlO)3ZrH
(AlO)3ZrH
(SiO)3HfH
(SiO)2HfH2
(SiO)Hf(Np)H2
(Si/AlO)3HfH
(AlO)3HfH
(SiO)2TaH
(SiO)2TaH(PMe3)
(AlO)2TaH
(ZrO)(SiO)TaH
(SiO)2WHn (n = 24)
(Si/AlO)2WHn (n = 24)
(AlO)2WHn (n = 24)
TiSiO2-H-1
TiASA-H-1
ZrSiO2-H-1
ZrSiO2-H-2
ZrASA-H-1
ZrAl2O3-H-1
HfSiO2-H-1
HfSiO2-H-2
HfSiO2-H-2-R-1
HfASA-H-1
HfAl2O3-H-1
TaSiO2-H-1
TaSiO2-H-1-P
TaAl2O3-H-1
TaZrO2/SiO2-H-1
WSiO2-H-n
WASA-H-n
WAl2O3-H-n
1706,1692,1679,1647
16001725
1633
1649, 1622
1635(br)
1622
1701
1720, 1675
1685, 1651
1702, 1675(sh)
1670
1830,1815(sh), 1855(sh)
1687
1830
1800
1960, 1815
1948,1819
1903, 1804
132
405
136,455457
457,458
406
459
460,461
461
461
142
462
299,463
454
373
464
465
409
373
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
3.4.1. Stoichiometric Ligand Exchange via Protonolysis Reactions with Brnsted Acids. Treatment of surface
alkyls, amides, hydrides, and other complexes with Brnsted
acids leads to substitution of the ligands via protonolysis and
gives the corresponding ligand exchanged products. This
methodology is widely applied to generate surface alkoxides
(Scheme 33), carboxylates, and acetylacetonates from welldened surface species.131,137,155,179,183,186,253,271,472474
3.4.2. Reactions with Lewis Bases. Small molecules such
as CO, CO2, and N2 are probes for post-treated surface sites.346
These probes have specic IR and NMR signatures that provide
detailed information about the structure of the surface site. In
addition, these signatures can be compared with literature
precedents, and now be reliably calculated using computational
methods.83,84,384 For instance, CO stretching, pyridine CC
vibration361,384,475 and 15N chemical shifts476478 provide direct
information about the nature (Lewis, Brnsted vs H-bonding)
and the strength of the acid sites. R3P or the oxide derivatives
can also be similarly used as probe molecules.479
3.4.3. Coordination and Activation of N2. N2 is a very
weak -donor ligand that binds to strong Lewis acid sites or
metals that have strong back-bonding properties.480,481 N2
binds to Al(III) defect sites on the surface of Al2O3 and has
a very distinctive IR signatures.360 N2 also binds (SiO)2TaH,
and reacts in the presence of H2 to split N2 to form (
SiO)2Ta(NH)(NH2) at a single metal center as shown in
Scheme 34.482,483 (SiO)2Ta(NH)(NH2) can be independently synthesized from reaction of (SiO)2TaH (TaSiO2H-1) with NH3.484 Computations suggest that coordination of
H2 decreases the energy of activation of N2 by avoiding changes
to the oxidation state of Ta.482
3.4.4. Activation of O2 and N2O. (SiO)3Ta (TaSiO2)
reacts with 0.5 equiv of O2 to yield the corresponding Ta(V)
oxo species, (SiO)3Ta(O) (TaSiO2-O) without the
detection of reaction intermediates (Scheme 35a).452 (
SiO)3ZrH (ZrSiO2-H-1) and (SiO)2ZrH2 (ZrSiO2-H-2), react
BC
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 14. Formation of WS2 from well-dened grafted W sites: inuence of the preparation method on the morphology and the hydrogenation
activity.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 38. Methane Activation on (a) ZrSiO2-H-1 and (b) by TaSiO2-H-1 and (c) Reaction of Cyclopentane with TaSiO2-H-1
BE
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
4.2.1. Alkene Metathesis Using Group 67 SilicaSupported Catalysts. Alkene metathesis was discovered 60
years ago using both homogeneous and heterogeneous
catalysts.8,95,494497 Chauvin proposed that metallocarbenes
and metallacyclobutanes were the key reaction intermediates of
olen metathesis.498,499 This insight ultimately led to the
development of homogeneous well-dened alkylidene catalysts
BF
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
the SP isomer (OtBuF9 < OtBuF6 < OtBuF3 < OSi(OtBu)3 <
OtBu).211,314,511,523,524 In this series, catalytic activity (TOF)
increases with decreasing -donation of the X-ligand.
A systematic investigation on the inuence of both the imido
and X ligands in (SiO)W(NAryl)(CHCMe2R)(X)
(Aryl = Ar, ArCl, ArCF3, and ArF5; X = OtBuF9, OtBuF6, OtBu,
OSi(OtBu)3, Me2Pyr; and R = Me or Ph) was recently
reported.314 The inuence of each member of the ligand set
was correlated to the TOF in cis-4-nonene self-metathesis using
multivariate linear regression analysis tools.525 The analysis
showed that the TOF of (SiO)W(NAryl)(CHCMe2R)(X) relates to the -donating character of the imido and X
ligands, evaluated by the NBO charge of the nitrogen atom in
ArylNH2 and the pKa of HX, respectively as well as the sterics
of the X ligand evaluated from the Sterimol B5 parameter (eq
1).314 This quantitative structureactivity relationship analysis
of the large series of well-dened heterogeneous catalysts
showed that high activity could be optimized by combination of
X and NAryl ligands of opposite electronic character and by a
simple and straightforward evaluation of the electronics and
sterics of the ligands from readily available parameters.314
TOF3min = 53.8 + 16.6(NBON,ArylNH2 /B5,HX )
+ 33.6(NBON,ArylNH2 /pK a,HX)
BG
(1)
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
the corresponding system grafted on silica partially dehydroxylated at 140200 C leads to unselective catalysts that catalyze
both alkyne metathesis and polymerization.547 This catalyst is
compatible with alkynes containing alkyl, aryl, benzoate,
thiophene, and methoxy substituents and can be recycled.
(SiO)W(CtBu)(OAr)2 (W-34m) is inactive in alkyne
metathesis at room temperature but becomes active at 80 C
with initial TOF of 0.32 molsub molW1 min1.324 The related
complex (SiO)W(CtBu)(CH2tBu)2 (W-33m) is inactive in
alkyne metathesis.323 In analogy to the example above, (
SiO)W2(NMe2)5 (W-2m) is also inactive in alkyne metathesis,
but its reaction with 5 equiv of tBuOH forms (SiO)W2
(NMe2)5n(OtBu)n (W-2m-OtBu) which equilibrates 4-nonyne
(50 equiv) in less than 30 min.158 However, control
experiments suggest that metathesis with this system probably
occurs in solution.
(SiO)Mo(N)(Py)(OSiMe3)(NMe2) (Mo-22m)548 catalyzes alkyne metathesis between 45 and 80 C with a sizable
induction period.325 This metal-nitrido complex probably reacts
with an alkyne to form the alkylidyne in situ. The addition of
B(C6F5)3 increases the initial rate of metathesis and reduces the
induction period observed in the absence of borane (Scheme
46). B(C6F5)3 assists the conversion of the MoN to the
Imidation of oxo complexes with isocyanates and N-sulnylamines is well-known in molecular chemistry549,550 and has
been used to probe the structure of surface oxo complexes of
Re,551 V,272,275 and Ta463 (Scheme 47a). Similarly, imido
complexes also participate in imido-transfer reactions with
aldehydes and other oxo-containing compounds, the stoichiometric reaction being demonstrated for supported V272,275 and
Ta268 imido complexes (Scheme 47b). Being combined, these
two transformations constitute a catalytic cycle referred to as
oxo/imido heterometathesis in analogy to olen metathesis
substrate
TON
Re2m
Mo-20mb
W-34ma
Mo-22mb
Mo-22m + 2 equiv B(C6F5)3b
MeCCEt
PhCCMe
MeCCEt
PhCCMe
PhCCMe
15
18
460
321
0.051
0.005
0.2
[22]
[24]
[80]
[45]
[110]
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
suggest that CH bond activation corresponds occurs via a bond metathesis,487 which is easier on dihydride than
monohydride surface species (Scheme 58c).458
Hydrogenolysis of alkanes is also observed in the presence of
H2 with Zr hydrides supported on alumina459 or aminemodied SBA15 (Scheme 57c,d).590,591 In this study the Zrdihydride linked through [N,O]-chelating surface ligands was
proposed to be more active than the analogous system linked
via [N,N]-ligands.
(SiO)2TaHx (Scheme 57b) also catalyze the hydrogenolysis of alkanes, including ethane in contrast to group 4
metals.592 In this case methane is the nal product for acyclic
alkanes. (SiO) 2TaHx also cleave the CC bond of
cycloalkanes to yield acyclic and cyclic products. These results
indicate that the hydrogenolysis mechanism must dier from
that of supported group 4 hydrides. The proposed mechanism
for (SiO)2TaHx with alkanes is shown in Scheme 59a. The
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
mediates metathesis, albeit with much lower TON (<40). Ta1b and W-1m and their methyl methylene derivatives Ta-1b150C were shown to be ecient catalyst precursors for alkane
metathesis, giving TON = 49 for Ta and TON = 120 for
W.144,150,605 The tungsten catalysts are typically more reactive
and more robust than those of tantalum. Ta-1b and W-1m
disproportionate linear alkanes,466 as well as catalyze the ring
opening metathesis of cyclooctane.561 Finally, silica-supported
WOCl4 activated by ZnMe2 also mediates the metathesis of
cyclooctane at 150 C, similar to other W-based catalysts.561
The proposed alkane metathesis mechanism466,606 is based
on the following evidence: alkenes are the primary products of
the reaction from ow kinetic studies,607 linear alkanes (Cn) are
transformed primarily into Cn+1 and Cn1, and the active metal
sites must be able to accommodate three anionic alkyl ligands.
These observations are consistent with a mechanism in which
CC bonds are formed and broken by alkene metathesis,
mediated by alkylidene hydride intermediates shown in Scheme
62.
In the proposed mechanism, tantalum hydride TaH-1
reacts with propane to form a tantalum propyl species. H
elimination from the propyl ligand, gives a Ta alkylidene
hydride intermediate. A series of alkane dehydrogenation and
alkene metathesis steps then complete the cycle. The alkylidene
hydride is multifunctional, able to perform both alkane
dehydrogenation and alkene metathesis, as shown in Scheme
62. The Cn+1 selectivity arises from the preferred formation of
1,3-disubstituted metallacyclobutanes (which give only Cn+1)
over 1,2-disubstituted metallacyclobutanes (Scheme 62).
Computational studies have shown that direct -bond metathesis between MR and alkane CC bonds is unlikely.595
Tantalum hydrides TaSiO2-H-1 and TaSiO2-H-3 can convert a
mixture of alkene and H2 into lower and higher alkanes. The
mechanism of this transformation is probably similar to that of
alkane/alkene metathesis.300
(SiO)3ZrH and (SiO)2ZrH2 do not show any metathesis reactivity with propane. However, under supercritical
conditions, silicaalumina supported zirconium hydrides
catalyze the metathesis of propane to form branched rather
than linear alkanes.608 Dialkyl species (SiO)2Zr(CH2tBu)2
(Zr-1b) gives similar rates and selectivities under the same
reaction conditions. The active site is probably the bis-hydride
(SiO)2ZrH2 (ZrASA-H-2). The proposed mechanism involves
the reaction of ZrASA-H-2 with alkanes to produce dialkyl Zr
species, [Zr(C3H7)2]. This species undergoes -alkyl transfer to
produce [Zr(C3H7) (Me)(C2H4)] (Scheme 63). This intermediate can then produce a variety of dierent products. For
instance, insertion of ethylene into the propyl ligand gives npentane. Alternatively, transfer of the -H of the propyl ligand
to the ethylene ligand (by -H transfer/insertion) makes
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 66. (a) Catalytic Epoxidation of Alkenes and (b) Epoxidation Catalysts
Cat.
Ti-6b
Ti-26t
Ti-10m
Ti-27tf
Ti-20m
Ta-9b
Ta-14tf
Mo-23m
Fe-8b/t
Fe-13m
Solvent
Decane
Toluene
Toluene
CH3CN
Octane
CH3CN
CH3CN
CH2Cl2
CH3CN
CH3CN
[O]
TBHP
CHP
CHP
H2O2
TBHP
H2O2
H2O2
TBHP
H2O2
H2O2
T (C)
Time (h)
50
65
65
65
60
65
65
40
25
60
16
2
1
2
8
3
2
2
1
1
Ca or Yb
a
98
24.5b
e
15.3a
54a
7.3a
7.4b
99.5a
71.5b
7.3a
Sel.c
TONd
Ref
100
>98
e
20.0
e
80g
98.4
98.9
45
24
62.5
176
643
116
633
132
83
957
64.8
2.6
185
615
193
617
263
266
617
326
199
243
a
Total conversion of peroxide (%). bEpoxide yield based on peroxide (%). cSelectivity for epoxidation product (%). dTON = mol epoxidation
product/mol metal. eno tabulated data available. fRcap = n-Bu. gepoxide + diol.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
was improved, with turnover numbers up to 2,000.193 Ligandfree catalysts were prepared by calcination of Ti-8m, 9m, and
10m and showed reduced activity, possibly due to migration of
the titanium centers into the support, making the catalytic sites
less accessible.193 In order to evaluate the eect of a dimeric Ti
precursor, [(tBuO)2Ti{-O2Si[OSi(OtBu)3]2}]2 was grafted on
SBA15130 to give Ti-11m epoxidation catalyst.195 Ti-11m has
similar activity and selectivity for cyclohexene epoxidation with
organic hydroperoxides as Ti-8m, 9m, and 10m. Several
parameters were suggested to determine high catalytic activity
of Ti catalysts including more Lewis acidic Ti sites formed from
Si-rich molecular compounds, tetrahedral Ti(IV) sites, suppressed nucleation to octahedral TiO2 and high dispersion of Ti
sites.193,195 Ti[OGe(iPr)3]4 on SBA15120 (Ti-12m) was
compared to the siloxide-only precursors for cyclohexene
oxidation with TBHP and found to produce 23 times higher
TONs after 9h under identical conditions.191 The activity and
selectivity of Ti-8m and Ti-11m in epoxidation using H2O2 can
be improved by capping surface OH groups with Me2N
SiMe2(R) (R = Me, n-Bu, or n-octyl, Scheme 67).616
When compared with uncapped Ti materials, species on
modied surfaces such as Ti-27t exhibit up to 58% selectivity
for cyclohexene oxide over the undesired allylic oxidation
products (Table 8, entry 4).616,617 Treating Ti-10m capped
with Me2NSiMe2(R) at 200 C under O2 exposes free Ti
OH.194 Modication of these titanols with phenols and
carboxylic acids results in 10 to 50% higher conversions and
selectivity of 1-octene epoxidation with TBHP or H2O2.194
Isolated Ti centers as well as oligomerized Ti species (TiO2
nanoclusters) could be prepared by grafting Ti(OiPr)4 on
mesoporous aluminophosphate (AlPO) supports that contain
reactive surface AlOH and POH groups.618 The catalytic
activity and selectivity of cyclohexene epoxidation with TiAlPO is slightly lower than that of Ti-SBA15 material with
comparable Ti loadings and using TBHP; additionally, Ti-AlPO
materials form more allylic oxidation products.618
The isolation of Ti sites could also be obtained by grafting
molecular precursors containing a large calixarene ligand. The
corresponding grafted complex Ti-20m displays a rigid
pseudotetrahedral geometry, and TONs up to 633 for the
BS
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Scheme 69. (a) Industrial Synthesis of Adipic Acid; (b) Catalytically Active Species and Their Activity in Cycloalkane
Oxidation; (c) Deperoxidation with M = Ti, R = tBu, H and M = Zr, Hf, R = tBu; (d) Benzylic Oxidation of Alkyl Aromatics;
and (e) Methane Oxidation
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
catalyst
S/Ca
time
(h)
conv.
(%)
1
2
3
4
5
6
7
8
(SiO)3HfOtBu
(SiO)3ZrOtBu
(SiO)3TiOtBu
(SiO)3TiNp3 + O2
(SiO)3TiOH
(SiO)Ta(OMe)4
(SiO)2Ta(OMe)3
(SiO)3Ta(OMe)2
260
350
260
312
252
270
250
240
6
6
6
6
6
6
9
8
30
40
88
77
87
88
66
88
sel.b
one/olc
0.7
0.84
0.72
1.5
1.3
0.9
a
Substrate/catalyst ratio. bSelectivity to cyclohexanone and cyclohexanol based on consumed cyclohexyl hydroperoxide. cCyclohexanone/cyclohexanol ratio.
Leaching of Ti is signicant (up to 30%), though hotltration tests showed that the desorbed species were not
responsible for the catalytic activity. In contrast, silicasupported alkoxo-tantalum complexes (SiO)nTa(OR)5-n (n
= 13) are stable toward leaching under identical reaction
BU
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 16. Templated formation of mesostructured hybrid organo-silica materials (ad), left; idealized regular distribution of organic moieties at the
silica surface and a representation of periodic mesoporous materials (right).
5. EMERGING FIELDS
5.1. Well-Dened Catalysts through Grafting on Advanced
Functional Materials
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Figure 17. Templated formation of periodic mesoporous organosilicas (left) and selected catalysts.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
6. CONCLUSIONS
Industrial heterogeneous catalysts are usually developed and
optimized by empirical approaches due to the complexity of
these materials. As shown in this review, the continuing
development of molecular chemistry and the advancement of
tools to characterize complex materials has allowed the
preparation of heterogeneous catalysts containing well-dened
active sites to emerge as an alternative and powerful strategy to
empirical methods. Understanding the surface chemistry of the
oxide support is a critical step to choose an adequate molecular
precursor for grafting because the surface determines the
binding of the metal site and promotes or hinders side
reactions. Generally, molecular precursors react with a surface
oxide OH group by protonolysis of a MX group, where X is
an appropriately reactive anionic ligand. In a few cases
alternative grafting pathways were uncovered, in particular for
molecular precursors containing multiply bonded ligands.
SiO 2700 is a nearly ideal support for well-dened
heterogeneous catalysts because it contains a low coverage of
mostly isolated silanols (ca. 0.8 OH nm2). On this support
most grafting reactions occur by protonolysis of an MX group
single-site catalysts discussed above. For example, posttreatment of well-dened surface species under pressures of
H2 can lead to the controlled growth of clusters and
nanoparticles with improved reactivity compared to supported
nanoparticles prepared from classical methods. The choice of
the molecular precursor is often essential to the resulting
particle size and the interface between the support and the
particle.168,213,381 The surge of research in electro- and
photocatalysis is also converging toward similar molecular
approaches where control of the structures of surface species is
critical for optimal catalytic behavior.424,429,665680 Outside of
catalysis, the benets of controlling the structures of surface
sites are rapidly becoming apparent in materials used in imaging
technologies.88,681683 The molecular approach is also nding
broad acceptance in the design and implementation of
nanocrystals684693 and functionalized nanoparticles or composites,448,694 where the control of surface chemistry has impacts
Figure 18. Idealized molecular representations of fragments of (a) bpy-Ir-UiO, (b) sal-Fe/Co-UiO, and (c) one-pot postsynthetic condensation to
Ni@(Fe)-MIL-10-NH2.
BX
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
ASSOCIATED CONTENT
S Supporting Information
*
AUTHOR INFORMATION
Corresponding Author
*E-mail: ccoperet@inorg.chem.ethz.ch.
Notes
Christophe Coperet was trained in chemistry and chemical engineering in CPE Lyon and then undertook a Ph.D. in chemistry at Purdue
University (USA) under the supervision of Prof. Negishi (1996). After
a postdoctoral stay in the group of Prof. Sharpless, he joined C2P2 (at
the time LCOMS) as a CNRS researcher in 1998 and was promoted
CNRS Research Director in 2008. Since 2010, he is Professor at the
Department of Chemistry at ETH Zurich. His research interest lies at
the interface of molecular, material, and surface chemistry with
applications in catalysis, energy, imaging, and microelectronics, and his
work relies on the combination of advanced spectroscopic methods
like surface enhanced NMR spectroscopy and computational
chemistry.
BY
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
ACKNOWLEDGMENTS
We are grateful to the Marie-Curie Fellowship program, SNF,
and ETHZ for nancial support. A.C.-V. thanks the SNF for
nancial support (Ambizione Project PZ00P2_148059). We
also thank Profs. M. Delferro, T. J. Marks, J. Sauer, C. Chizallet,
and P. Raybaud for sending us coordinates of some of the
systems to make suitable gures.
DEDICATION
This review is dedicated to the memory of Yu. I. Yermakov
(19351986), one of the pioneers of the eld, on the occasion
of the 80th anniversary of his birth.
ABBREVIATION LIST
SupportT subscript indicates temperature of dehydroxylation
of the support (e.g., SiO2700)
AS
Degussa Aerosil-200
SG
silica gel
IR
infrared spectroscopy
Raman
Raman spectroscopy
UVvis
UV and visible region spectroscopy
EA
elemental analysis
MB
mass balance analysis
TGA
thermogravimetric analysis
NMR
nuclear magnetic resonance spectroscopy
EPR
electron paramagnetic resonance spectroscopy
Magn
Magnetic Moment and Magnetic Susceptibility
Measurements
XPS
X-ray photoelectron spectroscopy
XANES
X-ray absorption near edge structure spectroscopy
EXAFS
extended X-ray absorption ne structure spectroscopy
EDX
energy-dispersive X-ray spectroscopy
Ar
2,6-iPr2C6H3
Ar
3,5-Me2C6H3
ArCl
2,6-Cl2C6H3
ArCF3
2-CF3C6H4
ArF5
C6F5
Ad
1-adamantyl
Mes
2,4,6-Me3C6H2
tBuF3
CMe2(CF3)
tBuF6
CMe(CF3)2
tBuF9
C(CF3)3
Pyr
pyrrolyl
Me2Pyr
2,5-dimethylpyrrolyl
dppz
3,5-diphenylpyrazolyl
dtpz
3,5-di-t-butylpyrazolyl
HMTO
2,6-Mes2C6H3O
HMTS
2,6-Mes2C6H3S
dAdPO
2,6-Ad2-4-MeC6H2O
DME
dimethoxyethane
DMF
N,N-dimethylformamide
CA
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
TMEDA
COD
COT
acac
fod
Review
N,N,N,N-tetramethylethylenediamine
1,5-cyclooctadiene
1,3,5,7-cyclooctatetraene
acetylacetonate
1,1,1,2,2,3,3-heptauoro-7,7-dimethyl-4,6-octanedione
REFERENCES
(1) Handbook of Heterogeneous Catalysis, 2 ed.; Ertl, G., Knozinger,
H., Schuth, F., Weitkamp, J., Eds.; Wiley-VCH Verlag GmbH:
Weinheim, Germany, 2008.
(2) Fine Chemicals through Heterogeneous Catalysis; Sheldon, R. A.,
van Bekkum, H., Eds.; Wiley-VCH Verlag GmbH: Weinheim,
Germany, 2007.
(3) Groppo, E.; Lamberti, C.; Bordiga, S.; Spoto, G.; Zecchina, A.
The Structure of Active Centers and the Ethylene Polymerization
Mechanism on the Cr/SiO2 Catalyst: A Frontier for the Characterization Methods. Chem. Rev. 2005, 105, 115184.
(4) Stalzer, M. M.; Delferro, M.; Marks, T. J. Supported Single-Site
Organometallic Catalysts for the Synthesis of High-Performance
Polyolefins. Catal. Lett. 2015, 145, 314.
(5) Sattler, J. J. H. B.; Ruiz-Martinez, J.; Santillan-Jimenez, E.;
Weckhuysen, B. M. Catalytic Dehydrogenation of Light Alkanes on
Metals and Metal Oxides. Chem. Rev. 2014, 114, 1061310653.
(6) Wachs, I. E.; Roberts, C. A. Monitoring Surface Metal Oxide
Catalytic Active Sites with Raman Spectroscopy. Chem. Soc. Rev. 2010,
39, 50025017.
(7) Ivin, K.; Mol, H. In Olen Metathesis and Metathesis Polymerization (2); Ivin, K. J., Mol, J. C., Eds.; Academic Press: London, 1997.
(8) Lwin, S.; Wachs, I. E. Olefin Metathesis by Supported Metal
Oxide Catalysts. ACS Catal. 2014, 4, 25052520.
(9) Buijink, J. K. F.; van Vlaanderen, J. J. M.; Crocker, M.; Niele, F.
G. M. Propylene Epoxidation over Titanium-on-Silica CatalystThe
Heart of the SMPO Process. Catal. Today 2004, 9395, 199204.
(10) Coperet, C.; Chabanas, M.; Petroff Saint-Arroman, R.; Basset, J.M. Homogeneous and Heterogeneous Catalysis: Bridging the Gap
through Surface Organometallic Chemistry. Angew. Chem., Int. Ed.
2003, 42, 156181.
(11) Candy, J.-P.; Coperet, C.; Basset, J.-M. Analogy between Surface
and Molecular Organometallic Chemistry. Top. Organomet. Chem.
2005, 16, 151210.
(12) Basset, J. M.; Candy, J. P.; Coperet, C. In Comprehensive
Organometallic Chemistry III; Crabtree, R. H., Mingos, D. M. P., Eds.;
Elsevier: Oxford, 2007; pp 499553.
(13) Modern Surface Organometallic Chemistry; Basset, J.-M., Psaro,
R., Roberto, D., Ugo, R., Eds.; Wiley-VCH Verlag GmbH & Co.
KGaA: Weinheim, Germany, 2009.
(14) Marks, T. J. Surface-Bound Metal Hydrocarbyls. Organometallic
Connections between Heterogeneous and Homogeneous Catalysis.
Acc. Chem. Res. 1992, 25, 5765.
(15) Wegener, S. L.; Marks, T. J.; Stair, P. C. Design Strategies for
the Molecular Level Synthesis of Supported Catalysts. Acc. Chem. Res.
2012, 45, 206214.
(16) Tada, M.; Iwasawa, Y. Advanced Design of Catalytically Active
Reaction Space at Surfaces for Selective Catalysis. Coord. Chem. Rev.
2007, 251, 27022716.
(17) Anwander, R. SOMC@PMS. Surface Organometallic Chemistry
at Periodic Mesoporous Silica. Chem. Mater. 2001, 13, 44194438.
(18) Liang, Y.; Anwander, R. Nanostructured Catalysts via Metal
Amide-Promoted Smart Grafting. Dalton Trans. 2013, 42, 12521
12545.
(19) Guzman, J.; Gates, B. C. Supported Molecular Catalysts: Metal
Complexes and Clusters on Oxides and Zeolites. Dalton Trans. 2003,
33033318.
(20) Serna, P.; Gates, B. C. Molecular Metal Catalysts on Supports:
Organometallic Chemistry Meets Surface Science. Acc. Chem. Res.
2014, 47, 26122620.
CB
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(66) Mathey, L.; Alphazan, T.; Valla, M.; Veyre, L.; Fontaine, H.;
Enyedi, V.; Yckache, K.; Danielou, M.; Kerdiles, S.; Guerrero, J.; et al.
Functionalization of Silica Nanoparticles and Native Silicon Oxide
with Tailored Boron-Molecular Precursors for Efficient and Predictive
p-Doping of Silicon. J. Phys. Chem. C 2015, 119, 1375013757.
(67) Lelli, M.; Gajan, D.; Lesage, A.; Caporini, M. A.; Vitzthum, V.;
Mieville, P.; Heroguel, F.; Rascon, F.; Roussey, A.; Thieuleux, C.; et al.
Fast Characterization of Functionalized Silica Materials by Silicon-29
Surface-Enhanced NMR Spectroscopy Using Dynamic Nuclear
Polarization. J. Am. Chem. Soc. 2011, 133, 21042107.
(68) Kobayashi, T.; Lafon, O.; Lilly Thankamony, A. S.; Slowing, I. I.;
Kandel, K.; Carnevale, D.; Vitzthum, V.; Vezin, H.; Amoureux, J.-P.;
Bodenhausen, G.; et al. Analysis of Sensitivity Enhancement by
Dynamic Nuclear Polarization in Solid-State NMR: A Case Study of
Functionalized Mesoporous Materials. Phys. Chem. Chem. Phys. 2013,
15, 55535562.
(69) Trebosc, J.; Wiench, J. W.; Huh, S.; Lin, V. S. Y.; Pruski, M.
Solid-State NMR Study of MCM-41-Type Mesoporous Silica
Nanoparticles. J. Am. Chem. Soc. 2005, 127, 30573068.
(70) Liu, C. C.; Maciel, G. E. The Fumed Silica Surface: A Study by
NMR. J. Am. Chem. Soc. 1996, 118, 51035119.
(71) Kerber, R. N.; Kermagoret, A.; Callens, E.; Florian, P.; Massiot,
D.; Lesage, A.; Coperet, C.; Delbecq, F. o.; Rozanska, X.; Sautet, P.
Nature and Structure of Aluminum Surface Sites Grafted on Silica
from a Combination of High-Field Aluminum-27 Solid-State NMR
Spectroscopy and First-Principles Calculations. J. Am. Chem. Soc. 2012,
134, 67676775.
(72) Valla, M.; Rossini, A. J.; Caillot, M.; Chizallet, C.; Raybaud, P.;
Digne, M.; Chaumonnot, A.; Lesage, A.; Emsley, L.; van Bokhoven, J.
A.; et al. Atomic Description of the Interface between Silica and
Alumina in Aluminosilicates through Dynamic Nuclear Polarization
Surface-Enhanced NMR Spectroscopy and First-Principles Calculations. J. Am. Chem. Soc. 2015, 137, 1071010719.
(73) Merle, N.; Trebosc, J.; Baudouin, A.; Rosal, I. D.; Maron, L.;
Szeto, K.; Genelot, M.; Mortreux, A.; Taoufik, M.; Delevoye, L.; et al.
17
O NMR Gives Unprecedented Insights into the Structure of
Supported Catalysts and Their Interaction with the Silica Carrier. J.
Am. Chem. Soc. 2012, 134, 92639275.
(74) Merle, N.; Girard, G.; Popoff, N.; De Mallmann, A.; Bouhoute,
Y.; Trebosc, J.; Berrier, E.; Paul, J. F.; Nicholas, C. P.; Del Rosal, I.;
et al. On the Track to Silica-Supported Tungsten Oxo Metathesis
Catalysts: Input from 17O Solid-State NMR. Inorg. Chem. 2013, 52,
1011910130.
(75) Perras, F. A.; Kobayashi, T.; Pruski, M. Natural Abundance 17O
DNP Two-Dimensional and Surface-Enhanced NMR Spectroscopy. J.
Am. Chem. Soc. 2015, 137, 83368339.
(76) Ashbrook, S. E.; Smith, M. E. Solid State O-17 NMR - An
Introduction to the Background Principles and Applications to
Inorganic Materials. Chem. Soc. Rev. 2006, 35, 718735.
(77) Quadrelli, E. A.; Basset, J.-M. On Silsesquioxanes Accuracy as
Molecular Models for Silica-Grafted Complexes in Heterogeneous
Catalysis. Coord. Chem. Rev. 2010, 254, 707728.
(78) Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Recent Developments
in the Chemistry of Cubic Polyhedral Oligosilsesquioxanes. Chem. Rev.
2010, 110, 20812173.
(79) Feher, F. J.; Budzichowski, T. A. Silasesquioxanes as Ligands in
Inorganic and Organometallic Chemistry. Polyhedron 1995, 14, 3239
3253.
(80) Feher, F. J.; Soulivong, D.; Nguyen, F. Practical Methods for
Synthesizing Four Incompletely Condensed Silsesquioxanes from a
Single R8Si8O12 Framework. Chem. Commun. 1998, 12791280.
(81) Lorenz, V.; Fischer, A.; Giemann, S.; Gilje, J. W.; Gunko, Y.;
Jacob, K.; Edelmann, F. T. Disiloxanediolates and Polyhedral
Metallasilsesquioxanes of the Early Transition Metals and f-Elements.
Coord. Chem. Rev. 2000, 206207, 321368.
(82) Duchateau, R. Incompletely Condensed Silsesquioxanes:
Versatile Tools in Developing Silica-Supported Olefin Polymerization
Catalysts. Chem. Rev. 2002, 102, 35253542.
CC
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(243) Roukoss, C.; Fiddy, S.; de Mallmann, A.; Rendon, N.; Basset, J.
M.; Kuntz, E.; Coperet, C. Access to Well-Defined Isolated Fe(II)
Centers on Silica and Their Use in Oxidation. Dalton Trans. 2007,
55465548.
(244) Huang, E. K.; Cheung, W. M.; Chan, K. W.; Lam, F. L. Y.; Hu,
X. J.; Zhang, Q. F.; Williams, I. D.; Leung, W. H. Alkylruthenium
Complexes Containing Polypyridyl Ligands: Synthesis, Characterization, and Immobilization on Silica. Eur. J. Inorg. Chem. 2013, 2013,
28932899.
(245) Brutchey, R. L.; Drake, I. J.; Bell, A. T.; Tilley, T. D. LiquidPhase Oxidation of Alkylaromatics by a H-Atom Transfer Mechanism
with a New Heterogeneous CoSBA-15 Catalyst. Chem. Commun.
2005, 37363738.
(246) Dorcier, A.; Merle, N.; Taoufik, M.; Bayard, F.; Lucas, C.; de
Mallmann, A.; Basset, J. M. Preparation of a Well-Defined SilicaSupported Nickel-Diimine Alkyl Complex Application for the GasPhase Polymerization of Ethylene. Organometallics 2009, 28, 2173
2178.
(247) Choi, Y. S.; Moschetta, E. G.; Miller, J. T.; Fasulo, M.;
McMurdo, M. J.; Rioux, R. M.; Tilley, T. D. Highly Dispersed PdSBA15 Materials from Tris(tert-butoxy)siloxy Complexes of Pd(II).
ACS Catal. 2011, 1, 11661177.
(248) Kaplan, A. W.; Bergman, R. G. Nitrous Oxide Mediated
Synthesis of Monomeric Hydroxoruthenium Complexes. Reactivity of
(DMPE)2Ru(H)(OH) and the Synthesis of a Silica-Bound Ruthenium
Complex. Organometallics 1998, 17, 50725085.
(249) Scott, S. L.; Szpakowicz, M.; Mills, A.; Santini, C. C. Ligand
Exchange and Oxidative Addition on a Silica-Supported Rhodium
Complex, trans-[(SiO)Rh(PMe3)2(CO)]. J. Am. Chem. Soc. 1998,
120, 18831890.
(250) Rimoldi, M.; Fodor, D.; van Bokhoven, J. A.; Mezzetti, A. A
Stable 16-Electron Iridium(III) Hydride Complex Grafted on SBA-15:
A Single-site Catalyst for Alkene Hydrogenation. Chem. Commun.
2013, 49, 1131411316.
(251) Richmond, M. K.; Scott, S. L.; Yap, G. P. A.; Alper, H.
Preparation of Dinuclear Phosphine-Bridged Palladium(II) Species
and Their Silica-Bound Analogues as Catalysts for the Cyclization of
Aminoalkynes. Organometallics 2002, 21, 33953400.
(252) Gajan, D.; Levine, D.; Zocher, E.; Coperet, C.; Lesage, A.;
Emsley, L. Probing Surface Site Heterogeneity through 1D and
INADEQUATE 31P Solid State NMR Spectroscopy of Silica
Supported PMe3-Au(I) Adducts. Chem. Sci. 2011, 2, 928931.
(253) Salinier, V.; Corker, J. M.; Lefebvre, F.; Bayard, F.; Dufaud, V.;
Basset, J.-M. Silica-Supported Zirconium Complexes and their
Polyoligosilsesquioxane Analogues in the Transesterification of
Acrylates: Part 1. Synthesis and Characterization. Adv. Synth. Catal.
2009, 351, 21552167.
(254) Silvennoinen, R. J.; Jylha, O. J. T.; Lindblad, M.; Sainio, J. P.;
Puurunen, R. L.; Krause, A. O. I. Atomic Layer Deposition of
Iridium(III) Acetylacetonate on Alumina, SilicaAlumina, and Silica
Supports. Appl. Surf. Sci. 2007, 253, 41034111.
(255) Hisamoto, M.; Nelson, R. C.; Lee, M.-Y.; Eckert, J.; Scott, S. L.
Mode of Adsorption of (CH3)2Au(acac) onto Partially Dehydroxylated Silica. J. Phys. Chem. C 2009, 113, 87948805.
(256) Abis, L.; Armelao, L.; Belli DellAmico, D.; Calderazzo, F.;
Garbassi, F.; Merigo, A.; Quadrelli, E. A. Gold Molecular Precursors
and GoldSilica Interactions. J. Chem. Soc., Dalton Trans. 2001, 2704
2709.
(257) Hascall, T.; Rheingold, A. L.; Guzei, I.; Parkin, G. Subvalent
Germanium and Tin Complexes Supported by a Dianionic Calixarene
Ligand: Structural Characterization of Exo and Endo Isomers of
[Butcalix(TMS)2]Ge. Chem. Commun. 1998, 101102.
(258) Buccella, D.; Parkin, G. p-tert-Butylcalix[4]arene Complexes of
Molybdenum and Tungsten: Reactivity of the Calixarene Methylene
C-H Bond and the Facile Migration of the Metal Around the Phenolic
Rim of the Calixarene. J. Am. Chem. Soc. 2006, 128, 1635816364.
(259) Buccella, D.; Parkin, G. Mononuclear and Dinuclear
Molybdenum and Tungsten Complexes of p-tertButyltetrathiacalix[4]arene and p-tert-Butyltetrasulfonylcalix[4]arene:
CH
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
atures through a Combined Use of Molecular and Surface Organometallic Chemistry. J. Organomet. Chem. 2006, 691, 54485455.
(294) Lesage, A.; Emsley, L.; Chabanas, M.; Coperet, C.; Basset, J.M. Observation of a H-Agostic Bond in a Highly Active Rhenium
Alkylidene Olefin Metathesis Heterogeneous Catalyst by TwoDimensional Solid-State NMR Spectroscopy. Angew. Chem., Int. Ed.
2002, 41, 45354538.
(295) Schultz, A. J.; Williams, J. M.; Schrock, R. R.; Rupprecht, G. A.;
Fellmann, J. D. Interaction of Hydrogen and Hydrocarbons with
Transition Metals. Neutron Diffraction Evidence for an Activated
Carbon-Hydrogen Bond in an Electron-Deficient Tantalum-Neopentylidene Complex. J. Am. Chem. Soc. 1979, 101, 15931595.
(296) Brookhart, M.; Green, M. L. H. Carbon-Hydrogen-Transition
Metal Bonds. J. Organomet. Chem. 1983, 250, 395408.
(297) Rhers, B.; Salameh, A.; Baudouin, A.; Quadrelli, E. A.; Taoufik,
M.; Coperet, C.; Lefebvre, F.; Basset, J. M.; Solans-Monfort, X.;
Eisenstein, O.; et al. A Well-Defined, Silica-Supported Tungsten Imido
Alkylidene Olefin Metathesis Catalyst. Organometallics 2006, 25,
35543557.
(298) Marciniec, B.; Rogalski, S.; Potrzebowski, M. J.; Pietraszuk, C.
Ruthenium Carbene Siloxide Complexes Immobilized on Silica:
Synthesis and Catalytic Activity in Olefin Metathesis. ChemCatChem
2011, 3, 904910.
(299) Soignier, S.; Taoufik, M.; Le Roux, E.; Saggio, G.; Dablemont,
C.; Baudouin, A.; Lefebvre, F.; de Mallmann, A.; Thivolle-Cazat, J.;
Basset, J.-M.; et al. Tantalum Hydrides Supported on MCM-41
Mesoporous Silica: Activation of Methane and Thermal Evolution of
the Tantalum-Methyl Species. Organometallics 2006, 25, 15691577.
(300) Polshettiwar, V.; Thivolle-Cazat, J.; Taoufik, M.; Stoffelbach,
F.; Norsic, S.; Basset, J. M. Hydro-Metathesis of Olefins: a Catalytic
Reaction Using a Bifunctional Single-Site Tantalum Hydride Catalyst
Supported on Fibrous Silica (KCC-1) Nanospheres. Angew. Chem., Int.
Ed. 2011, 50, 27472751.
(301) Chabanas, M.; Baudouin, A.; Coperet, C.; Basset, J. M. A
Highly Active Well-Defined Rhenium Heterogeneous Catalyst for
Olefin Metathesis Prepared via Surface Organometallic Chemistry. J.
Am. Chem. Soc. 2001, 123, 20622063.
(302) Chabanas, M.; Coperet, C.; Basset, J. M. Re-Based
Heterogeneous Catalysts for Olefin Metathesis Prepared by Surface
Organometallic Chemistry: Reactivity and Selectivity. Chem. - Eur. J.
2003, 9, 971975.
(303) Blanc, F.; Coperet, C.; Thivolle-Cazat, J.; Basset, J. M.; Lesage,
A.; Emsley, L.; Sinha, A.; Schrock, R. R. Better Characterization of
Surface Organometallic Catalysts through Resolution Enhancement in
Proton Solid State NMR Spectra. Inorg. Chem. 2006, 45, 95879592.
(304) Leduc, A. M.; Salameh, A.; Soulivong, D.; Chabanas, M.;
Basset, J. M.; Coperet, C.; Solans-Monfort, X.; Clot, E.; Eisenstein, O.;
Bohm, V. P. W.; et al. -H Transfer from the Metallacyclobutane: A
Key Step in the Deactivation and Byproduct Formation for the WellDefined Silica-Supported Rhenium Alkylidene Alkene Metathesis
Catalyst. J. Am. Chem. Soc. 2008, 130, 62886297.
(305) Blanc, F.; Coperet, C.; Thivolle-Cazat, J.; Basset, J. M.; Lesage,
A.; Emsley, L.; Sinha, A.; Schrock, R. R. Surface Versus Molecular
Siloxy Ligands in Well-Defined Olefin Metathesis Catalysts:
[{(RO)3SiO}Mo(NAr)(CHtBu) (CH2tBu)]. Angew. Chem., Int.
Ed. 2006, 45, 12161220.
(306) Blanc, F.; Salameh, A.; Thivolle-Cazat, J.; Basset, J. M.;
Coperet, C.; Sinha, A.; Schrock, R. R. Grafting Mechanism and Olefin
Metathesis Activity of Well-Defined Silica-Supported Mo Imido Alkyl
Alkylidene Complexes. C. R. Chim. 2008, 11, 137146.
(307) Blanc, F.; Thivolle-Cazat, J.; Basset, J. M.; Coperet, C.; Hock,
A. S.; Tonzetich, Z. J.; Schrock, R. R. Highly Active, Stable, and
Selective Well-Defined Silica Supported Mo Imido Olefin Metathesis
Catalysts. J. Am. Chem. Soc. 2007, 129, 10441045.
(308) Blanc, F.; Berthoud, R.; Salameh, A.; Basset, J. M.; Coperet, C.;
Singh, R.; Schrock, R. R. Dramatic Improvements of Well-Defined
Silica Supported Mo-Based Olefin Metathesis Catalysts by Tuning the
N-Containing Ligands. J. Am. Chem. Soc. 2007, 129, 84348435.
(309) Rendon, N.; Berthoud, R.; Blanc, F.; Gajan, D.; Maishal, T.;
Basset, J. M.; Coperet, C.; Lesage, A.; Emsley, L.; Marinescu, S. C.;
et al. Well-Defined Silica-Supported Mo-Alkylidene Catalyst Precursors Containing One OR Substituent: Methods of Preparation and
Structure-Reactivity Relationship in Alkene Metathesis. Chem. - Eur. J.
2009, 15, 50835089.
(310) Gajan, D.; Rendon, N.; Wampler, K. M.; Jean-Marie, B.;
Coperet, C.; Lesage, A.; Emsley, L.; Schrock, R. R. Synthesis and
Reactivity of Molybdenum Imido Alkylidene Bis-Pyrazolide Complexes. Dalton Trans. 2010, 39, 85478551.
(311) Blanc, F.; Rendon, N.; Berthoud, R.; Basset, J.-M.; Coperet, C.;
Tonzetich, Z. J.; Schrock, R. R. Dramatic Enhancement of the Alkene
Metathesis Activity of Mo Imido Alkylidene Complexes upon
Replacement of One tBuO by a Surface Siloxy Ligand. Dalton Trans.
2008, 31563158.
(312) Balcar, H.; Z ilkova, N.; Sedlace k, J.; Zednk, J. MCM-41
Anchored Schrock Catalyst Mo(CHCMe2Ph)(N-2,6-i-Pr2C6H3)[OCMe(CF3)2]2-Activity in 1-Heptene Metathesis and Cross-Metathesis Reactions. J. Mol. Catal. A: Chem. 2005, 232, 5358.
(313) Blanc, F.; Berthoud, R.; Coperet, C.; Lesage, A.; Emsley, L.;
Singh, R.; Kreickmann, T.; Schrock, R. R. Direct Observation of
Reaction Intermediates for a Well Defined Heterogeneous Alkene
Metathesis Catalyst. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 12123
12127.
(314) Mougel, V.; Santiago, C. B.; Zhizhko, P. A.; Bess, E. N.; Varga,
J.; Frater, G.; Sigman, M. S.; Coperet, C. Quantitatively Analyzing
Metathesis Catalyst Activity and Structural Features in SilicaSupported Tungsten Imido-Alkylidene Complexes. J. Am. Chem. Soc.
2015, 137, 66996704.
(315) Allouche, F.; Mougel, V.; Coperet, C. Activating ThiolateBased Imidoalkylidene Tungsten(VI) Metathesis Catalysts by Grafting
onto Silica. Asian J. Org. Chem. 2015, 4, 528532.
(316) Conley, M. P.; Mougel, V.; Peryshkov, D. V.; Forrest, W. P.,
Jr.; Gajan, D.; Lesage, A.; Emsley, L.; Coperet, C.; Schrock, R. R. A
Well-Defined Silica-Supported Tungsten Oxo Alkylidene Is a Highly
Active Alkene Metathesis Catalyst. J. Am. Chem. Soc. 2013, 135,
1906819070.
(317) Conley, M. P.; Forrest, W. P.; Mougel, V.; Coperet, C.;
Schrock, R. R. Bulky Aryloxide Ligand Stabilizes a Heterogeneous
Metathesis Catalyst. Angew. Chem., Int. Ed. 2014, 53, 1422114224.
(318) Mougel, V.; Pucino, M.; Coperet, C. Strongly Donating
Thiophenoxide in Silica-Supported Tungsten Oxo Catalysts for
Improved 1-Alkene Metathesis Efficiency. Organometallics 2015, 34,
551554.
(319) Herrmann, W. A.; Stumpf, A. W.; Priermeier, T.; Bogdanovic,
S.; Dufaud, V.; Basset, J.-M. A Molecularly Defined, Grafted Olefin
Metathesis Catalyst from Tris(neopentyl)-nitridomolybdenum(VI).
Angew. Chem., Int. Ed. Engl. 1996, 35, 28032805.
(320) Blanc, F.; Chabanas, M.; Coperet, C.; Fenet, B.; Herdweck, E.
Reactivity Differences Between Molecular and Surface Silanols in the
Preparation of Homogeneous and Heterogeneous Olefin Metathesis
Catalysts. J. Organomet. Chem. 2005, 690, 50145026.
(321) Saint-Arroman, R. P.; Chabanas, M.; Baudouin, A.; Coperet,
C.; Basset, J.-M.; Lesage, A.; Emsley, L. Characterization of Surface
Organometallic Complexes Using High Resolution 2D Solid-State
NMR Spectroscopy. Application to the Full Characterization of a Silica
Supported Metal Carbyne: SiOMo(CBu-t) (CH2Bu-t)2. J.
Am. Chem. Soc. 2001, 123, 38203821.
(322) Weissman, H.; Plunkett, K. N.; Moore, J. S. A Highly Active,
Heterogeneous Catalyst for Alkyne Metathesis. Angew. Chem., Int. Ed.
2006, 45, 585588.
(323) Le Roux, E.; Taoufik, M.; Chabanas, M.; Alcor, D.; Baudouin,
A.; Coperet, C.; Thivolle-Cazat, J.; Basset, J.-M.; Lesage, A.; Hediger,
S.; et al. Well-Defined Surface Tungstenocarbyne Complexes through
the Reaction of [W(CtBu) (CH2tBu)3] with Silica. Organometallics
2005, 24, 42744279.
(324) Merle, N.; Taoufik, M.; Nayer, M.; Baudouin, A.; Le Roux, E.;
Gauvin, R. M.; Lefebvre, F.; Thivolle-Cazat, J.; Basset, J. M.
Development of a Well-Defined Silica-Supported Tungstenocarbyne
CJ
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(363) Digne, M.; Sautet, P.; Raybaud, P.; Euzen, P.; Toulhoat, H.
Hydroxyl Groups on Gamma-Alumina Surfaces: A DFT Study. J.
Catal. 2002, 211, 15.
(364) Digne, M.; Sautet, P.; Raybaud, P.; Euzen, P.; Toulhoat, H. Use
of DFT to Achieve a Rational Understanding of Acid-Basic Properties
of -Alumina Surfaces. J. Catal. 2004, 226, 5468.
(365) Ferreira, A. R.; Martins, M. J. F.; Konstantinova, E.; Capaz, R.
B.; Souza, W. F.; Chiaro, S. S. X.; Leitao, A. A. Direct Comparison
between Two Structural Models by DFT Calculations. J. Solid State
Chem. 2011, 184, 11051111.
(366) Comas-Vives, A.; Schwarzwalder, M.; Coperet, C.; Sautet, P.
CarbonCarbon Bond Formation by Activation of CH3F on Alumina.
J. Phys. Chem. C 2015, 119, 71567163.
(367) Comas-Vives, A.; Valla, M.; Coperet, C.; Sautet, P.
Cooperativity between Al Sites Promotes Hydrogen Transfer and
CarbonCarbon Bond Formation upon Dimethyl Ether Activation on
Alumina. ACS Cent. Sci. 2015, 1, 313.
(368) Nortier, P.; Fourre, P.; Saad, A. B. M.; Saur, O.; Lavalley, J. C.
Effects of Crystallinity and Morphology on the Surface Properties of
Alumina. Appl. Catal. 1990, 61, 141160.
(369) Kovarik, L.; Genc, A.; Wang, C.; Qiu, A.; Peden, C. H. F.;
Szanyi, J.; Kwak, J. H. Tomography and High-Resolution Electron
Microscopy Study of Surfaces and Porosity in a Plate-like -Al2O3. J.
Phys. Chem. C 2013, 117, 179186.
(370) Joubert, J.; Delbecq, F.; Sautet, P.; Le Roux, E.; Taoufik, M.;
Thieuleux, C.; Blanc, F.; Coperet, C.; Thivolle-Cazat, J.; Basset, J. M.
Molecular Understanding of Alumina Supported Single-Site Catalysts
by a Combination of Experiment and Theory. J. Am. Chem. Soc. 2006,
128, 91579169.
(371) Delgado, M.; Santini, C. C.; Delbecq, F.; Wischert, R.;
Guennic, B. L.; Tosin, G.; Spitz, R.; Basset, J.-M.; Sautet, P. Alumina as
a Simultaneous Support and Co Catalyst: Cationic Hafnium Complex
Evidenced by Experimental and DFT Analyses. J. Phys. Chem. C 2010,
114, 1851618528.
(372) Delgado, M.; Delbecq, F.; Santini, C. C.; Lefebvre, F.; Norsic,
S.; Putaj, P.; Sautet, P.; Basset, J.-M. Evolution of Structure and of
Grafting Properties of -Alumina with Pretreatment Temperature. J.
Phys. Chem. C 2012, 116, 834843.
(373) Taoufik, M.; Le Roux, E.; Thivolle-Cazat, J.; Coperet, C.;
Basset, J.-M.; Maunders, B.; Sunley, G. J. Alumina Supported Tungsten
Hydrides, New Efficient Catalysts for Alkane Metathesis. Top. Catal.
2006, 40, 6570.
(374) Le Roux, E.; Taoufik, M.; Coperet, C.; de Mallmann, A.;
Thivolle-Cazat, J.; Basset, J. M.; Maunders, B. M.; Sunley, G. J.
Development of Tungsten-Based Heterogeneous Alkane Metathesis
Catalysts Through a StructureActivity Relationship. Angew. Chem.,
Int. Ed. 2005, 44, 67556758.
(375) Yuan, J.; Townsend, E. M.; Schrock, R. R.; Goldman, A. S.;
Muller, P.; Takase, M. K. Preparation of Tungsten-Based Olefin
Metathesis Catalysts Supported on Alumina. Adv. Synth. Catal. 2011,
353, 19851992.
(376) Herrmann, W. A.; Kuhn, F. E. Organorhenium Oxides. Acc.
Chem. Res. 1997, 30, 169180.
(377) Salameh, A.; Joubert, J.; Baudouin, A.; Lukens, W.; Delbecq, F.;
Sautet, P.; Basset, J. M.; Coperet, C. CH3ReO3 on Gamma-Al2O3:
Understanding Its Structure, Initiation, and Reactivity in Olefin
Metathesis. Angew. Chem., Int. Ed. 2007, 46, 38703873.
(378) Wischert, R.; Coperet, C.; Delbecq, F.; Sautet, P. Revisiting the
Structure of Methyltrioxorhenium Chemisorbed on Alumina. ChemCatChem 2010, 2, 812815.
(379) Veljanovski, D. Ph.D. Technische Universitat Munchen, 2009.
(380) Trovitch, R. J.; Guo, N.; Janicke, M. T.; Li, H.; Marshall, C. L.;
Miller, J. T.; Sattelberger, A. P.; John, K. D.; Baker, R. T. Spectroscopic
Characterization of Alumina-Supported Bis(allyl)iridium Complexes:
Site-Isolation, Reactivity, and Decomposition Studies. Inorg. Chem.
2010, 49, 22472258.
(381) Heroguel, F.; Siddiqi, G.; Detwiler, M. D.; Zemlyanov, D. Y.;
Safonova, O. V.; Coperet, C. Simultaneous Generation of Mild Acidic
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(401) Chizallet, C.; Raybaud, P. Acidity of Amorphous SilicaAlumina: From Coordination Promotion of Lewis Sites to Proton
Transfer. ChemPhysChem 2010, 11, 105108.
(402) Leydier, F.; Chizallet, C.; Chaumonnot, A.; Digne, M.; Soyer,
E.; Quoineaud, A.-A.; Costa, D.; Raybaud, P. Brnsted Acidity of
Amorphous SilicaAlumina: The Molecular Rules of Proton Transfer.
J. Catal. 2011, 284, 215229.
(403) Moses, A. W.; Ramsahye, N. A.; Raab, C.; Leifeste, H. D.;
Chattopadhyay, S.; Chmelka, B. F.; Eckert, J.; Scott, S. L.
Methyltrioxorhenium Interactions with Lewis Acid Sites of an
Amorphous SilicaAlumina. Organometallics 2006, 25, 21572165.
(404) Moses, A. W.; Raab, C.; Nelson, R. C.; Leifeste, H. D.;
Ramsahye, N. A.; Chattopadhyay, S.; Eckert, J.; Chmelka, B. F.; Scott,
S. L. Spectroscopically Distinct Sites Present in Methyltrioxorhenium
Grafted onto Silica-Alumina, and Their Abilities to Initiate Olefin
Metathesis. J. Am. Chem. Soc. 2007, 129, 89128920.
(405) Larabi, C.; Merle, N.; Norsic, S. b.; Taoufik, M.; Baudouin, A.;
Lucas, C.; Thivolle-Cazat, J.; de Mallmann, A.; Basset, J.-M. Surface
Organometallic Chemistry of Titanium on SilicaAlumina and
Catalytic Hydrogenolysis of Waxes at Low Temperature. Organometallics 2009, 28, 56475655.
(406) Dufaud, V.; Basset, J.-M. Catalytic Hydrogenolysis at Low
Temperature and Pressure of Polyethylene and Polypropylene to
Diesels or Lower Alkanes by a Zirconium Hydride Supported on
Silica-Alumina: A Step Toward Polyolefin Degradation by the
Microscopic Reverse of Ziegler-Natta Polymerization. Angew. Chem.,
Int. Ed. 1998, 37, 806810.
(407) Norsic, S.; Larabi, C.; Delgado, M.; Garron, A.; de Mallmann,
A.; Santini, C.; Szeto, K. C.; Basset, J.-M.; Taoufik, M. Low
Temperature Hydrogenolysis of Waxes to Diesel Range Gasoline
and Light Alkanes: Comparison of Catalytic Properties of Group 4, 5
and 6 Metal Hydrides Supported on SilicaAlumina. Catal. Sci.
Technol. 2012, 2, 215219.
(408) Szeto, K. C.; Hardou, L.; Merle, N.; Basset, J. M.; ThivolleCazat, J.; Papaioannou, C.; Taoufik, M. Selective Conversion of
Butane into Liquid Hydrocarbon Fuels on Alkane Metathesis
Catalysts. Catal. Sci. Technol. 2012, 2, 13361339.
(409) Le Roux, E.; Taoufik, M.; Baudouin, A.; Coperet, C.; ThivolleCazat, J.; Basset, J. M.; Maunders, B. M.; Sunley, G. J. Silica-AluminaSupported, Tungsten-Based Heterogeneous Alkane Metathesis Catalyst: Is It Closer to a Silica- or an Alumina-Supported System? Adv.
Synth. Catal. 2007, 349, 231237.
(410) Samantaray, M. K.; Dey, R.; Abou-Hamad, E.; Hamieh, A.;
Basset, J. M. Effect of Support on Metathesis of n-Decane: Drastic
Improvement in Alkane Metathesis with WMe5 Linked to SilicaAlumina. Chem. - Eur. J. 2015, 21, 61006106.
(411) Che, M.; Tench, A. J. Characterization and Reactivity of
Mononuclear Oxygen Species on Oxide Surfaces. Adv. Catal. 1982, 31,
77133.
(412) Chizallet, C.; Costentin, G.; Lauron-Pernot, H.; Che, M.;
Bonhomme, C.; Maquet, J.; Delbecq, F.; Sautet, P. Study of the
Structure of OH Groups on MgO by 1D and 2D H-1 MAS NMR
Combined with DFT Cluster Calculations. J. Phys. Chem. C 2007, 111,
1827918287.
(413) Chizallet, C.; Costentin, G.; Che, M.; Delbecq, F.; Sautet, P.
Infrared Characterization of Hydroxyl Groups on MgO: A Periodic
and Cluster Density Functional Theory Study. J. Am. Chem. Soc. 2007,
129, 64426452.
(414) Knozinger, E.; Jacob, K.-H.; Singh, S.; Hofmann, P. Hydroxyl
Groups as IR Active Surface Probes on MgO Crystallites. Surf. Sci.
1993, 290, 388402.
(415) Khabuanchalad, S.; Wittayakun, J.; Lobo-Lapidus, R. J.; Stoll,
S.; Britt, R. D.; Gates, B. C. Formation of MgO-Supported Manganese
Carbonyl Complexes by Chemisorption of Mn(CO)5CH3. Langmuir
2013, 29, 62796286.
(416) Bhirud, V. A.; Ehresmann, J. O.; Kletnieks, P. W.; Haw, J. F.;
Gates, B. C. Rhodium Complex with Ethylene Ligands Supported on
Highly Dehydroxylated MgO: Synthesis, Characterization, and
Reactivity. Langmuir 2006, 22, 490496.
(417) Uzun, A.; Ortalan, V.; Browning, N. D.; Gates, B. C. SiteIsolated Iridium Complexes on MgO Powder: Individual Ir Atoms
Imaged by Scanning Transmission Electron Microscopy. Chem.
Commun. 2009, 46574659.
(418) Uzun, A.; Ortalan, V.; Browning, N. D.; Gates, B. C. A SiteIsolated Mononuclear Iridium Complex Catalyst Supported on MgO:
Characterization by Spectroscopy and Aberration-Corrected Scanning
Transmission Electron Microscopy. J. Catal. 2010, 269, 318328.
(419) Guzman, J.; Gates, B. C. Structure and Reactivity of a
Mononuclear Gold-Complex Catalyst Supported on Magnesium
Oxide. Angew. Chem., Int. Ed. 2003, 42, 690693.
(420) Iwasawa, Y.; Sato, H. Preparations of TiO2-Attached Rh
Catalysts and Their Catalysis. Chem. Lett. 1985, 507510.
(421) Guzman, J.; Kuba, S.; Fierro-Gonzalez, J.; Gates, B. Formation
of Gold Clusters on TiO2 from Adsorbed Au(CH3)2(C5H7O2):
Characterization by X-ray Absorption Spectroscopy. Catal. Lett. 2004,
95, 7786.
(422) Aguilar-Guerrero, V.; Gates, B. C. Genesis of a Highly Active
Cerium Oxide-Supported Gold Catalyst for CO Oxidation. Chem.
Commun. 2007, 32103212.
(423) Arrouvel, C.; Digne, M.; Breysse, M.; Toulhoat, H.; Raybaud,
P. Effects of Morphology on Surface Hydroxyl Concentration: A DFT
Comparison of AnataseTiO2 and -Alumina Catalytic Supports. J.
Catal. 2004, 222, 152166.
(424) Gratzel, M. Recent Advances in Sensitized Mesoscopic Solar
Cells. Acc. Chem. Res. 2009, 42, 17881798.
(425) Kato, M.; Zhang, J. Z.; Paul, N.; Reisner, E. Protein Film
Photoelectrochemistry of the Water Oxidation Enzyme Photosystem
II. Chem. Soc. Rev. 2014, 43, 64856497.
(426) Vannucci, A. K.; Alibabaei, L.; Losego, M. D.; Concepcion, J. J.;
Kalanyan, B.; Parsons, G. N.; Meyer, T. J. Crossing the Divide between
Homogeneous and Heterogeneous Catalysis in Water Oxidation. Proc.
Natl. Acad. Sci. U. S. A. 2013, 110, 2091820922.
(427) Alibabaei, L.; Sherman, B. D.; Norris, M. R.; Brennaman, M.
K.; Meyer, T. J. Visible Photoelectrochemical Water Splitting into H2
and O2 in a Dye-Sensitized Photoelectrosynthesis Cell. Proc. Natl.
Acad. Sci. U. S. A. 2015, 112, 58995902.
(428) Ganduglia-Pirovano, M. V.; Da Silva, J. L. F.; Sauer, J. DensityFunctional Calculations of the Structure of Near-Surface Oxygen
Vacancies and Electron Localization on CeO2(111). Phys. Rev. Lett.
2009, 102, 026101.
(429) Sheehan, S. W.; Thomsen, J. M.; Hintermair, U.; Crabtree, R.
H.; Brudvig, G. W.; Schmuttenmaer, C. A. A Molecular Catalyst for
Water Oxidation that Binds to Metal Oxide Surfaces. Nat. Commun.
2015, 6, 6469.
(430) Sozzani, P.; Bracco, S.; Comotti, A.; Simonutti, R.; Camurati, I.
Stoichiometric Compounds of Magnesium Dichloride with Ethanol for
the Supported Ziegler-Natta Catalysis: First Recognition and Multidimensional MAS NMR Study. J. Am. Chem. Soc. 2003, 125, 12881
12893.
(431) Malizia, F.; Fait, A.; Cruciani, G. Crystal Structures of Ziegler
Natta Catalyst Supports. Chem. - Eur. J. 2011, 17, 1389213897.
(432) Forte, M. C.; Coutinho, F. M. B. Highly Active Magnesium
Chloride Supported Ziegler-Natta Catalysts with Controlled Morphology. Eur. Polym. J. 1996, 32, 223231.
(433) Seenivasan, K.; Sommazzi, A.; Bonino, F.; Bordiga, S.; Groppo,
E. Spectroscopic Investigation of Heterogeneous ZieglerNatta
Catalysts: Ti and Mg Chloride Tetrahydrofuranates, Their Interaction
Compound, and the Role of the Activator. Chem. - Eur. J. 2011, 17,
86488656.
(434) Sobota, P. Metal-Assembled Compounds: Precursors of
Polymerization Catalysts and New Materials. Coord. Chem. Rev.
2004, 248, 10471060.
(435) Grau, E.; Lesage, A.; Norsic, S.; Coperet, C.; Monteil, V.;
Sautet, P. Tetrahydrofuran in TiCl4/THF/MgCl2: a Non-Innocent
Ligand for Supported Ziegler-Natta Polymerization Catalysts. ACS
Catal. 2013, 3, 5256.
(436) Groppo, E.; Gallo, E.; Seenivasan, K.; Lomachenko, K. A.;
Sommazzi, A.; Bordiga, S.; Glatzel, P.; van Silfhout, R.; Kachatkou, A.;
CM
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
Bras, W.; et al. XAS and XES Techniques Shed Light on the Dark Side
of ZieglerNatta Catalysts: Active-Site Generation. ChemCatChem
2015, 7, 14321437.
(437) Morra, E.; Giamello, E.; Van Doorslaer, S.; Antinucci, G.;
DAmore, M.; Busico, V.; Chiesa, M. Probing the Coordinative
Unsaturation and Local Environment of Ti3+ Sites in an Activated
High-Yield ZieglerNatta Catalyst. Angew. Chem., Int. Ed. 2015, 54,
48574860.
(438) Hino, M.; Kobayashi, S.; Arata, K. Solid Catalyst Treated with
Anion. 2. Reactions of Butane and Isobutane Catalyzed by Zirconium
Oxide Treated with Sulfate Ion. Solid Superacid Catalyst. J. Am. Chem.
Soc. 1979, 101, 64396441.
(439) Hino, M.; Arata, K. Synthesis of Solid Superacid Catalyst with
Acid Strength of H0 16.04. J. Chem. Soc., Chem. Commun. 1980,
851852.
(440) Drago, R. S.; Kob, N. Acidity and Reactivity of Sulfated
Zirconia and Metal-Doped Sulfated Zirconia. J. Phys. Chem. B 1997,
101, 33603364.
(441) Farcasiu, D.; Ghenciu, A.; Li, J. Q. The Mechanism of
Conversion of Saturated Hydrocarbons Catalyzed by Sulfated Metal
Oxides: Reaction of Adamantane on Sulfated Zirconia. J. Catal. 1996,
158, 116127.
(442) Haase, F.; Sauer, J. The Surface Structure of Sulfated Zirconia:
Periodic ab Initio Study of Sulfuric Acid Adsorbed on ZrO2(101) and
ZrO2(001). J. Am. Chem. Soc. 1998, 120, 1350313512.
(443) Hofmann, A.; Sauer, J. Surface Structure of Hydroxylated and
Sulfated Zirconia. A Periodic Density-Functional Study. J. Phys. Chem.
B 2004, 108, 1465214662.
(444) Williams, L. A.; Marks, T. J. Synthesis, Characterization, and
Heterogeneous Catalytic Implementation of Sulfated Alumina Nanoparticles. Arene Hydrogenation and Olefin Polymerization Properties
of Supported Organozirconium Complexes. ACS Catal. 2011, 1, 238
245.
(445) Gu, W.; Stalzer, M. M.; Nicholas, C. P.; Bhattacharyya, A.;
Motta, A.; Gallagher, J. R.; Zhang, G.; Miller, J. T.; Kobayashi, T.;
Pruski, M.; et al. Benzene Selectivity in Competitive Arene
Hydrogenation: Effects of Single-Site CatalystAcidic Oxide Surface
Binding Geometry. J. Am. Chem. Soc. 2015, 137, 67706780.
(446) Williams, L. A.; Guo, N.; Motta, A.; Delferro, M.; Fragala, I. L.;
Miller, J. T.; Marks, T. J. Surface Structural-Chemical Characterization
of a Single-Site d0 Heterogeneous Arene Hydrogenation Catalyst
Having 100% Active Sites. Proc. Natl. Acad. Sci. U. S. A. 2013, 110,
413418.
(447) Ahn, H.; Nicholas, C. P.; Marks, T. J. Surface Organozirconium
Electrophiles Activated by Chemisorption on Super Acidic Sulfated
Zirconia as Hydrogenation and Polymerization Catalysts. A Synthetic,
Structural, and Mechanistic Catalytic Study. Organometallics 2002, 21,
17881806.
(448) Nicholas, C. P.; Marks, T. J. Sulfated Tin Oxide Nanoparticles
as Supports for Molecule-Based Olefin Polymerization Catalysts. Nano
Lett. 2004, 4, 15571559.
(449) Nicholas, C. P.; Ahn, H.; Marks, T. J. Synthesis, Spectroscopy,
and Catalytic Properties of Cationic Organozirconium Adsorbates on
Super Acidic Sulfated Alumina. Single-Site Heterogeneous
Catalysts with Virtually 100% Active Sites. J. Am. Chem. Soc. 2003,
125, 43254331.
(450) Ruddy, D. A.; Tilley, T. D. Highly Selective Olefin Epoxidation
with Aqueous H2O2 over Surface-Modified TaSBA15 Prepared via the
TMP Method. Chem. Commun. 2007, 33503352.
(451) Holmes, S. A.; Quignard, F.; Choplin, A.; Teissier, R.;
Kervennal, J. Tetraneopentyltitanium Derived Silica Supported
Complexes - Part 2. Influence of the Hydrophobic Character of Silica
on the Catalytic Properties. J. Catal. 1998, 176, 182191.
(452) Saggio, G.; de Mallmann, A.; Maunders, B.; Taoufik, M.;
Thivolle-Cazat, J.; Basset, J.-M. Synthesis, Characterization, and
Reactivity of the Highly Unsaturated Silica-Supported Trisiloxy
Tantalum: (SiO)3Ta(III). Organometallics 2002, 21, 51675171.
(453) Quignard, F.; Choplin, A.; Teissier, R. A Molecular Route
towards Silica Supported Zirconium Catalysts Active for the Mild
CN
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(469) Berthoud, R.; Baudouin, A.; Fenet, B.; Lukens, W.; Pelzer, K.;
Basset, J.-M.; Candy, J.-P.; Coperet, C. Mononuclear Ruthenium
Hydride Species versus Ruthenium Nanoparticles: The Effect of Silane
Functionalities on Silica Surfaces. Chem. - Eur. J. 2008, 14, 35233526.
(470) Yermakov, Y. I.; Kuznetsov, B. N.; Startsev, A. N.; Zhdan, P.
A.; Shepelin, A. P.; Zaikovskii, V. I.; Plyasova, L. M.; Burmistrov, V. A.
Composition and Catalytic Activity of Supported Sulphided Metal
Catalysts Prepared via Anchored Complexes I. Tungsten Catalysts
Prepared via Anchoring of W(C4H7)4 on SiO2. J. Mol. Catal. 1981, 11,
205214.
(471) Yermakov, Y. I.; Startsev, A. N.; Burmistrov, V. A. Sulphide
Catalysts on Silica as a Support. I. Effect of the Preparation Technique
of (Ni,W)/SiO2 and (Ni,Mo)/SiO2 Catalysts on Their Activity in
Thiophen Hydrogenolysis. Appl. Catal. 1984, 11, 113.
(472) Meunier, D.; de Mallmann, A.; Basset, J.-M. Asymmetric
Epoxidation of Allylic Alcohols Catalyzed by (SiO)xTa(OEt)3x
(Dialkyl Tartrate Diolate): Influence of the Reaction Conditions.
Top. Catal. 2003, 23, 183189.
(473) Liang, Y.; Anwander, R. Organometallic Chemistry on Periodic
Mesoporous Organosilicas: Generation of Surface-Confined Zinc and
Yttrium Centres. Dalton Trans. 2006, 19091918.
(474) Leyrit, P.; McGill, C.; Quignard, F.; Choplin, A. A Novel
Heterogeneous Molecular Catalyst for the Meerwein-Ponndorf-Verley
and Oppenauer Reactions. J. Mol. Catal. A: Chem. 1996, 112, 395
400.
(475) Corma, A.; Garca, H. Lewis Acids: From Conventional
Homogeneous to Green Homogeneous and Heterogeneous Catalysis.
Chem. Rev. 2003, 103, 43074366.
(476) Maciel, G. E.; Haw, J. F.; Chuang, I. S.; Hawkins, B. L.; Early,
T. A.; McKay, D. R.; Petrakis, L. NMR Studies of Pyridine on SilicaAlumina. J. Am. Chem. Soc. 1983, 105, 55295535.
(477) Haw, J. F.; Chuang, I. S.; Hawkins, B. L.; Maciel, G. E. Surface
Titration of Silica-Alumina Monitored by Nitrogen-15 NMR with
Cross Polarization and Magic-Angle Spinning. J. Am. Chem. Soc. 1983,
105, 72067207.
(478) Ripmeester, J. A. Surface Acid Site Characterization by Means
of CP/MAS Nitrogen-15 NMR. J. Am. Chem. Soc. 1983, 105, 2925
2927.
(479) Osegovic, J. P.; Drago, R. S. Measurement of the Global
Acidity of Solid Acids by 31P MAS NMR of Chemisorbed
Triethylphosphine Oxide. J. Phys. Chem. B 2000, 104, 147154.
(480) Allen, A. D.; Harris, R. O.; Loescher, B. R.; Stevens, J. R.;
Whiteley, R. N. Dinitrogen Complexes of the Transition Metals. Chem.
Rev. 1973, 73, 1120.
(481) Fryzuk, M. D.; Johnson, S. A. The Continuing Story of
Dinitrogen Activation. Coord. Chem. Rev. 2000, 200202, 379409.
(482) Solans-Monfort, X.; Chow, C.; Goure, E.; Kaya, Y.; Basset, J.M.; Taoufik, M.; Quadrelli, E. A.; Eisenstein, O. Successive Heterolytic
Cleavages of H2 Achieve N2 Splitting on Silica-Supported Tantalum
Hydrides: A DFT Proposed Mechanism. Inorg. Chem. 2012, 51, 7237
7249.
(483) Avenier, P.; Taoufik, M.; Lesage, A.; Solans-Monfort, X.;
Baudouin, A.; de Mallmann, A.; Veyre, L.; Basset, J. M.; Eisenstein, O.;
Emsley, L.; et al. Dinitrogen Dissociation on an Isolated Surface
Tantalum Atom. Science 2007, 317, 10561060.
(484) Avenier, P.; Lesage, A.; Taoufik, M.; Baudouin, A.; De
Mallmann, A.; Fiddy, S.; Vautier, M.; Veyre, L.; Basset, J.-M.; Emsley,
L.; et al. Well-Defined Surface Imido Amido Tantalum(V) Species
from Ammonia and Silica-Supported Tantalum Hydrides. J. Am. Chem.
Soc. 2007, 129, 176186.
(485) Vidal, V.; Theolier, A.; Thivolle-Cazat, J.; Basset, J.-M.
Activation and Functionalisation of the C-H Bonds of Methane and
Higher Alkanes by a Silica-Supported Tantalum Hydride Complex. J.
Chem. Soc., Chem. Commun. 1995, 991992.
(486) Lecuyer, C.; Quignard, F.; Choplin, A.; Olivier, D.; Basset, J.M. Surface Organometallic Chemistry on Oxides: Selective Catalytic
Low-Temperature Hydrogenolysis of Alkanes by a Highly Electrophilic Zirconium Hydride Complex Supported on Silica. Angew. Chem.,
Int. Ed. Engl. 1991, 30, 16601661.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(525) Milo, A.; Neel, A. J.; Toste, F. D.; Sigman, M. S. A DataIntensive Approach to Mechanistic Elucidation Applied to Chiral
Anion Catalysis. Science 2015, 347, 737743.
(526) Mol, J. C.; Woerlee, E. F. G. Heterogeneous Metathesis of
Alkenes Having Functional-Groups. J. Chem. Soc., Chem. Commun.
1979, 330331.
(527) Edrevakardjieva, R. M.; Andreev, A. A. Formation of the Active
Form of Re2O7/SiO2 Catalyst in Olefin Metathesis. J. Catal. 1986, 97,
321329.
(528) Kirlin, P. S.; Gates, B. C. A Stable Supported Re Metathesis
Catalyst Derived from [Re(CO)3OH]4 on SiO2. J. Chem. Soc., Chem.
Commun. 1985, 277279.
(529) Duquette, L. G.; Cieslinski, R. C.; Jung, C. W.; Garrou, P. E.
ESCA Studies on Silica-Supported and Alumina-Supported Rhenium
Oxide Catalysts. J. Catal. 1984, 90, 362365.
(530) Tsuda, N.; Fujimori, A. Metathesis of Propylene over
Unsupported Rhenium Trioxide. J. Catal. 1981, 69, 410417.
(531) Vicente, B. C.; Nelson, R. C.; Moses, A. W.; Chattopadhyay, S.;
Scott, S. L. Interactions Involving Lewis Acidic Aluminum Sites in
Oxide-Supported Perrhenate Catalysts. J. Phys. Chem. C 2011, 115,
90129024.
(532) Herrmann, W. A.; Wagner, W.; Flessner, U. N.; Volkhardt, U.;
Komber, H. Methyltrioxorhenium as Catalyst for Olefin Metathesis.
Angew. Chem., Int. Ed. Engl. 1991, 30, 16361638.
(533) Buffon, R.; Choplin, A.; Leconte, M.; Basset, J. M.; Touroude,
R.; Herrmann, W. A. Surface Organometallic Chemistry of Rhenium:
Attempts to Characterize a Surface Carbene in Metathesis of Olefins
with the Catalyst CH3ReO3/Nb2O5. J. Mol. Catal. 1992, 72, L7L10.
(534) Rost, A. M. J.; Schneider, H.; Zoller, J. P.; Herrmann, W. A.;
Kuhn, F. E. Methyltrioxorhenium Heterogenized on Commercially
Available Supporting Materials as Cyclooctene Metathesis Catalyst. J.
Organomet. Chem. 2005, 690, 47124718.
(535) Salameh, A.; Baudouin, A.; Basset, J. M.; Coperet, C. Tuning
the Selectivity of Alumina-Supported (CH3)ReO3 by Modifying the
Surface Properties of the Support. Angew. Chem., Int. Ed. 2008, 47,
21172120.
(536) Salameh, A.; Baudouin, A.; Soulivong, D.; Boehm, V.; Roeper,
M.; Basset, J. M.; Coperet, C. CH3-ReO3 on -Al2O3: Activity,
Selectivity, Active Site and Deactivation in Olefin Metathesis. J. Catal.
2008, 253, 180190.
(537) Valla, M.; Conley, M. P.; Coperet, C. MeReO3/Al2O3 and
Me4Sn-Activated Re2O7/Al2O3 Alkene Metathesis Catalysts Have
Similar Active Sites. Catal. Sci. Technol. 2015, 5, 14381442.
(538) Tovar, T. M.; Stewart, S. M.; Scott, S. L. Origin of the ZnCl2
Effect on CH3ReO3/-Al2O3 in Olefin Metathesis. Top. Catal. 2012,
55, 530537.
(539) Mazoyer, E.; Szeto, K. C.; Merle, N.; Norsic, S.; Boyron, O.;
Basset, J.-M.; Taoufik, M.; Nicholas, C. P. Study of Ethylene/2-Butene
Cross-Metathesis over W-H/Al2O3 for Propylene Production: Effect of
the Temperature and Reactant Ratios on the Productivity and
Deactivation. J. Catal. 2013, 301, 17.
(540) Szeto, K. C.; Mazoyer, E.; Merle, N.; Norsic, S.; Basset, J. M.;
Nicholas, C. P.; Taoufik, M. Metallacyclobutane Substitution and Its
Effect on Alkene Metathesis for Propylene Production over W-H/
Al2O3: Case of Isobutene/2-Butene Cross-Metathesis. ACS Catal.
2013, 3, 21622168.
(541) Pennella, F.; Banks, R. L.; Bailey, G. C. Disproportionation of
Alkynes. Chem. Commun. 1968, 15481549.
(542) Katz, T. J.; McGinnis, J. Mechanism of the Olefin Metathesis
Reaction. J. Am. Chem. Soc. 1975, 97, 15921594.
(543) Wengrovius, J. H.; Sancho, J.; Schrock, R. R. Metathesis of
Acetylenes by Tungsten(VI)-Alkylidyne Complexes. J. Am. Chem. Soc.
1981, 103, 39323934.
(544) Freudenberger, J. H.; Schrock, R. R.; Churchill, M. R.;
Rheingold, A. L.; Ziller, J. W. Metathesis of Acetylenes by
(Fluoroalkoxy)Tungstenacyclobutadiene Complexes and the Crystal
Structure of W(C3Et3)[OCH(CF3)2]3. A Higher Order Mechanism
for Acetylene Metathesis. Organometallics 1984, 3, 15631573.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
(656) Manna, K.; Zhang, T.; Carboni, M.; Abney, C. W.; Lin, W.
Salicylaldimine-Based Metal-Organic Framework Enabling Highly
Active Olefin Hydrogenation with Iron and Cobalt Catalysts. J. Am.
Chem. Soc. 2014, 136, 1318213185.
(657) Falkowski, J. M.; Sawano, T.; Zhang, T.; Tsun, G.; Chen, Y.;
Lockard, J. V.; Lin, W. Privileged Phosphine-Based Metal-Organic
Frameworks for Broad-Scope Asymmetric Catalysis. J. Am. Chem. Soc.
2014, 136, 52135216.
(658) Canivet, J.; Aguado, S.; Schuurman, Y.; Farrusseng, D. MOFSupported Selective Ethylene Dimerization Single-Site Catalysts
through One-Pot Postsynthetic Modification. J. Am. Chem. Soc.
2013, 135, 41954198.
(659) Kaur, P.; Hupp, J. T.; Nguyen, S. T. Porous Organic Polymers
in Catalysis: Opportunities and Challenges. ACS Catal. 2011, 1, 819
835.
(660) Tanabe, K. K.; Siladke, N. A.; Broderick, E. M.; Kobayashi, T.;
Goldston, J. F.; Weston, M. H.; Farha, O. K.; Hupp, J. T.; Pruski, M.;
Mader, E. A.; et al. Stabilizing Unstable Species through Single-Site
Isolation: A Catalytically Active TaV Trialkyl in a Porous Organic
Polymer. Chem. Sci. 2013, 4, 24832489.
(661) Totten, R. K.; Weston, M. H.; Park, J. K.; Farha, O. K.; Hupp,
J. T.; Nguyen, S. T. Catalytic Solvolytic and Hydrolytic Degradation of
Toxic Methyl Paraoxon with La(catecholate)-Functionalized Porous
Organic Polymers. ACS Catal. 2013, 3, 14541459.
(662) Kraft, S. J.; Zhang, G.; Childers, D.; Dogan, F.; Miller, J. T.;
Nguyen, S. T.; Hock, A. S. Rhodium Catechol Containing Porous
Organic Polymers: Defined Catalysis for Single-Site and Supported
Nanoparticulate Materials. Organometallics 2014, 33, 25172522.
(663) Tanabe, K. K.; Ferrandon, M. S.; Siladke, N. A.; Kraft, S. J.;
Zhang, G.; Niklas, J.; Poluektov, O. G.; Lopykinski, S. J.; Bunel, E. E.;
Krause, T. R.; et al. Discovery of Highly Selective Alkyne
Semihydrogenation Catalysts Based on First-Row Transition-Metallated Porous Organic Polymers. Angew. Chem., Int. Ed. 2014, 53,
1205512058.
(664) Camacho-Bunquin, J.; Siladke, N. A.; Zhang, G.; Niklas, J.;
Poluektov, O. G.; Nguyen, S. T.; Miller, J. T.; Hock, A. S. Synthesis
and Catalytic Hydrogenation Reactivity of a Chromium Catecholate
Porous Organic Polymer. Organometallics 2015, 34, 947952.
(665) Li, W.; Sheehan, S. W.; He, D.; He, Y.; Yao, X.; Grimm, R. L.;
Brudvig, G. W.; Wang, D. Hematite-Based Solar Water Splitting in
Acidic Solutions: Functionalization by Mono- and Multilayers of
Iridium Oxygen-Evolution Catalysts. Angew. Chem., Int. Ed. 2015, 54,
1142811432.
(666) Oregan, B.; Gratzel, M. A Low-Cost, High-Efficiency Solar-Cell
Based On Dye-Sensitized Colloidal TiO2 Films. Nature 1991, 353,
737740.
(667) Ahmad, S.; Guillen, E.; Kavan, L.; Gratzel, M.; Nazeeruddin,
M. K. Metal Free Sensitizer and Catalyst for Dye Sensitized Solar
Cells. Energy Environ. Sci. 2013, 6, 34393466.
(668) Linsebigler, A. L.; Lu, G. Q.; Yates, J. T. Photocatalysis on
TiO2 Surfaces - Principles, Mechanisms, and Selected Results. Chem.
Rev. 1995, 95, 735758.
(669) Bard, A. J. Inner-Sphere Heterogeneous Electrode Reactions.
Electrocatalysis and Photocatalysis: The Challenge. J. Am. Chem. Soc.
2010, 132, 75597567.
(670) Andreiadis, E. S.; Jacques, P.-A.; Tran, P. D.; Leyris, A.;
Chavarot-Kerlidou, M.; Jousselme, B.; Matheron, M.; Pecaut, J.;
Palacin, S.; Fontecave, M.; et al. Molecular engineering of a cobaltbased electrocatalytic nanomaterial for H2 evolution under fully
aqueous conditions. Nat. Chem. 2013, 5, 4853.
(671) Le Goff, A.; Artero, V.; Jousselme, B.; Tran, P. D.; Guillet, N.;
Metaye, R.; Fihri, A.; Palacin, S.; Fontecave, M. From Hydrogenases to
Noble MetalFree Catalytic Nanomaterials for H2 Production and
Uptake. Science 2009, 326, 13841387.
(672) Schrauben, J. N.; Hayoun, R.; Valdez, C. N.; Braten, M.;
Fridley, L.; Mayer, J. M. Titanium and Zinc Oxide Nanoparticles Are
Proton-Coupled Electron Transfer Agents. Science 2012, 336, 1298
1301.
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
Review
CU
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX