Inorganic Chemistry
Article
Silica-Supported Niobium Complex Pairs Enhancing Catalytic Cyclic
Abou-Hamad, E.; Goh, S.; Samantaray, M.; Dey, R.; Cavallo, L.;
Carbonate Production. J. Am. Chem. Soc. 2015, 137, 7728−7739.
Basset, J.-M. Well-Defined Surface Species [(Si-O-)W(O)Me ]
3
(
11) Barman, S.; Maity, N.; Bhatte, K.; Ould-Chikh, S.; Dachwald,
Prepared by Direct Methylation of [(Si-O-)W(O)Cl ], a Catalyst
3
O.; Haeßner, C.; Saih, Y.; Abou-Hamad, E.; Llorens, I.; Hazemann, J.-
L.; Kohler, K.; D’ Elia, V.; Basset, J.-M. Single-Site VO Moieties
for Cycloalkane Metathesis and Transformation of Ethylene to
Propylene. ACS Catal. 2015, 5, 2164−2171.
̈
x
Generated on Silica by Surface Organometallic Chemistry: A Way To
Enhance the Catalytic Activity in the Oxidative Dehydrogenation of
Propane. ACS Catal. 2016, 6, 5908−5921.
(16) Schowner, R.; Frey, W.; Buchmeiser, M. R. Cationic Tungsten-
Oxo-Alkylidene-N-Heterocyclic Carbene Complexes: Highly Active
Olefin Metathesis Catalysts. J. Am. Chem. Soc. 2015, 137, 6188−6191.
(
12) (a) Rhers, B.; Salameh, A.; Baudouin, A.; Quadrelli, E. A.;
̈
(17) Peryshkov, D. V.; Schrock, R. R.; Takase, M. K.; Muller, P.;
Taoufik, M.; Coperet, C.; Lefebvre, F.; Basset, J. M.; Solans-Monfort,
X.; Eisenstein, O.; Lukens, W. W.; Lopez, L. P. H.; Sinha, A.; Schrock,
R. R. A Well-Defined, Silica-Supported Tungsten Imido Alkylidene
Olefin Metathesis Catalyst. Organometallics 2006, 25, 3554−3557.
Hoveyda, A. H. Z-Selective Olefin Metathesis Reactions Promoted by
Tungsten Oxo Alkylidene Complexes. J. Am. Chem. Soc. 2011, 133,
20754−20757.
(18) (a) Ibrahem, I.; Yu, M.; Schrock, R. R.; Hoveyda, A. H. Highly
Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions
Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes. J. Am.
Chem. Soc. 2009, 131, 3844−3845. (b) Flook, M. M.; Jiang, A. J.;
(
b) Coperet, C. Design and Understanding of Heterogeneous Alkene
Metathesis Catalysts. Dalton Trans. 2007, 5498−5505. (c) 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, 1044−1045. (d) 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, 8434−8435. (e) Mougel, V.; Santiago, C. B.;
Zhizhko, P. A.; Bess, E. N.; Varga, J.; Frater, G.; Sigman, M. S.;
̈
Schrock, R. R.; Muller, P.; Hoveyda, A. H. Z-Selective Olefin
Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylter-
phenoxide Monopyrrolide Complex. J. Am. Chem. Soc. 2009, 131,
7962−7963. (c) Flook, M. M.; Ng, V. W. L.; Schrock, R. R. Synthesis
of cis,syndiotactic ROMP Polymers Containing Alternating Enan-
tiomers. J. Am. Chem. Soc. 2011, 133, 1784−1786. (d) Jiang, A. J.;
Zhao, Y.; Schrock, R. R.; Hoveyda, A. H. Highly Z-Selective Metathesis
Homocoupling of Terminal Olefins. J. Am. Chem. Soc. 2009, 131,
16630−16631. (e) Marinescu, S. C.; Levine, D. S.; Zhao, Y.; Schrock,
R. R.; Hoveyda, A. H. Isolation of Pure Disubstituted E Olefins
through Mo-Catalyzed Z-Selective Ethenolysis of Stereoisomeric
Mixtures. J. Am. Chem. Soc. 2011, 133, 11512−11514. (f) Malcolmson,
S. J.; Meek, S. J.; Sattely, E. S.; Schrock, R. R.; Hoveyda, A. H. Highly
Efficient Molybdenum-based Catalysts for Enantioselective Alkene
Metathesis. Nature 2008, 456, 933−937. (g) Meek, S. J.; O’Brien, R.
V.; Llaveria, J.; Schrock, R. R.; Hoveyda, A. H. Catalytic Z-selective
Olefin Cross-metathesis for Natural Product Synthesis. Nature 2011,
471, 461−466. (h) Yu, M.; Wang, C.; Kyle, A. F.; Jakubec, P.; Dixon,
D. J.; Schrock, R. R.; Hoveyda, A. H. Synthesis of Macrocyclic Natural
Products by Catalyst-controlled Stereoselective Ring-closing Meta-
thesis. Nature 2011, 479, 88−93.
́
Coperet, C. Quantitatively Analyzing Metathesis Catalyst Activity and
Structural Features in Silica-Supported Tungsten Imido−Alkylidene
Complexes. J. Am. Chem. Soc. 2015, 137, 6699−6704. (f) Mougel, V.;
Coperet, C. Magnitude and Consequences of OR Ligand σ-Donation
on Alkene Metathesis Activity in d0 Silica Supported (SiO)W-
(
NAr)(CH-t-Bu)(OR) catalysts. Chem. Sci. 2014, 5, 2475−2481.
(13) (a) Mazoyer, E.; Merle, N.; Mallmann, A. D.; Basset, J.-M.;
Berrier, E.; Delevoye, L.; Paul, J.-F.; Nicholas, C. P.; Gauvin, R. M.;
Taoufik, M. Development of the First Well-Defined Tungsten Oxo
Alkyl Derivatives Supported on Silica by SOMC: Towards a Model of
WO /SiO2 Olefin Metathesis Catalyst. Chem. Commun. 2010, 46,
3
8
944−8946. (b) Bouhoute, Y.; Grekov, D.; Szeto, K. C.; Merle, N.; De
Mallmann, A.; Lefebvre, F.; Raffa, G.; Del Rosal, I.; Maron, L.; Gauvin,
R. M.; Delevoye, L.; Taoufik, M. Accessing Realistic Models for the
WO −SiO Industrial Catalyst through the Design of Organometallic
(19) Tamm, M.; Randoll, S.; Bannenberg, T.; Herdtweck, E.
Titanium Complexes with Imidazolin-2-iminato Ligands. Chem.
Commun. 2004, 876−877.
(20) Nomura, K.; Bahuleyan, B. K.; Tsutsumi, K.; Igarashi, A.
Synthesis of (Imido)vanadium(V) Alkyl and Alkylidene Complexes
Containing Imidazolidin-2-iminato Ligands: Effect of Imido Ligand on
ROMP and 1,2-C−H Bond Activation of Benzene. Organometallics
2014, 33, 6682−6691.
(21) (a) Tamm, M.; Randoll, S.; Herdtweck, E.; Kleigrewe, N.; Kehr,
G.; Erker, G.; Rieger, B. Imidazolin-2-iminato Titanium Complexes:
Synthesis, Structure and Use in Ethylene Polymerization Catalysis.
Dalton Trans. 2006, 459−467. (b) Shoken, D.; Sharma, M.;
Botoshansky, M.; Tamm, M.; Eisen, M. S. Mono(imidazolin-2-
iminato) Titanium Complexes for Ethylene Polymerization at Low
Amounts of Methylaluminoxane. J. Am. Chem. Soc. 2013, 135, 12592−
12595. (c) Nomura, K.; Bahuleyan, B. K.; Zhang, S.; Sharma, P. M. V.;
Katao, S.; Igarashi, A.; Inagaki, A.; Tamm, M. Synthesis and Structural
Analysis of (Imido)vanadium(V) Dichloride Complexes Containing
Imidazolin-2-iminato- and Imidazolidin-2-iminato Ligands, and their
Use as Catalyst Precursors for Ethylene (Co)polymerization. Inorg.
Chem. 2014, 53, 607−623.
(22) Trambitas, A. G.; Melcher, D.; Hartenstein, L.; Roesky, P. W.;
Daniliuc, C.; Jones, P. G.; Tamm, M. Bis(imidazolin-2-iminato) Rare
Earth Metal Complexes: Synthesis, Structural Characterization, and
Catalytic Application. Inorg. Chem. 2012, 51, 6753−6761.
(23) (a) Beer, S.; Hrib, C. G.; Jones, P. G.; Brandhorst, K.;
Grunenberg, J.; Tamm, M. Efficient Room-Temperature Alkyne
Metathesis with Well-Defined Imidazolin-2-iminato Tungsten Alkyli-
dyne Complexes. Angew. Chem., Int. Ed. 2007, 46, 8890−8894.
(b) Beer, S.; Brandhorst, K.; Hrib, C. G.; Wu, X.; Haberlag, B.;
Grunenberg, J.; Jones, P. G.; Tamm, M. Experimental and Theoretical
Investigations of Catalytic Alkyne Cross-Metathesis with Imidazolin-2-
3
2
Precursors. ACS Catal. 2016, 6, 1−18.
(
14) (a) 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, 14221−14224.
(
b) Mougel, V.; Pucino, M.; Coperet, C. Strongly σ Donating
Thiophenoxide in Silica-Supported Tungsten Oxo Catalysts for
Improved 1-Alkene Metathesis Efficiency. Organometallics 2015, 34,
5
51−554. (c) Conley, M. P.; Mougel, V.; Peryshkov, D. V.; Forrest, W.
P.; 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,
1
9068−19070. (d) Merle, N.; Girard, G.; Popoff, N.; Mallmann, A. D.;
Bouhoute, Y.; Trebosc, J.; Berrier, E.; Paul, J.-F.; Nicholas, C. P.; Rosal,
I. D.; Maron, L.; Gauvin, R. M.; Delevoye, L.; Taoufik, M. On the
Track to Silica-Supported Tungsten Oxo Metathesis Catalysts: Input
from 17O Solid-State NMR. Inorg. Chem. 2013, 52, 10119−10130.
(
e) Grekov, D.; Bouhoute, Y.; Szeto, K. C.; Merle, N.; De Mallmann,
A.; Lefebvre, F.; Lucas, C.; Del Rosal, I.; Maron, L.; Gauvin, R. M.;
Delevoye, L.; Taoufik, M. Silica-Supported Tungsten Neosilyl Oxo
Precatalysts: Impact of the Podality on Activity and Stability in Olefin
Metathesis. Organometallics 2016, 35, 2188−2196. (f) Pucino, M.;
Mougel, V.; Schowner, R.; Fedorov, A.; Buchmeiser, M. R.; Coperet,
C. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo
Alkylidene Sites: Highly Activeand Stable Catalysts for Olefin
Metathesis. Angew. Chem., Int. Ed. 2016, 55, 4300−4302.
(
15) (a) Bouhoute, Y.; Garron, A.; Grekov, D.; Merle, N.; Szeto, K.
C.; De Mallmann, A.; Del Rosal, I.; Maron, L.; Girard, G.; Gauvin, R.
M.; Delevoye, L.; Taoufik, M. Well-Defined Supported Mononuclear
Tungsten Oxo Species as Olefin Metathesis Pre-Catalysts. ACS Catal.
2
014, 4, 4232−4241. (b) Hamieh, A.; Chen, Y.; Abdel-Azeim, S.;
J
Inorg. Chem. XXXX, XXX, XXX−XXX