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Reactivity of a Silica-Supported Mo Alkylidene Catalyst toward Alkanes: A DFT Study on the Metathesis of Propane

dc.creatorDíaz E.spa
dc.creatorRestrepo A.spa
dc.creatorNúñez-Zarur F.spa
dc.date.accessioned2018-10-31T13:44:22Z
dc.date.available2018-10-31T13:44:22Z
dc.date.created2018
dc.identifier.issn2767333
dc.identifier.urihttp://hdl.handle.net/11407/4890
dc.descriptionThe metathesis of alkanes is a process in which a given alkane is transformed into higher and lower homologues. Here, we carried out DFT calculations in order to get insights into the most favorable reaction pathway for the metathesis of propane into mainly ethane and butane catalyzed by a silica-supported molybdenum alkylidene bearing an imido ligand at 150 °C. The overall catalytic process is divided into two stages, precursor activation and catalytic cycle, and both of them consist of the same types of reactions, (i) ligand exchange, (ii) proton transfer between two ?-carbons, and (iii) ligand rearrangement, which in turn consists of several steps, such as ?-H elimination, alkene cross-metathesis, and alkene insertion. Our results suggest that the formal ligand exchange reaction with propane proceeds through a dissociative mechanism with the formation of a high-energy molybdenum alkylidyne species. The calculated energetics at 150 °C indicates that the active species is a molybdenum propylidene species that is formed with an overall Gibbs activation barrier of 39.4 kcal mol-1. The catalytic cycle to the main products (ethane and butane) has an energy span of 43 kcal mol-1, whereas the cycle for the production of minor products (methane and pentane) has a much higher energy span, in agreement with experiments. These data suggest that the catalytic cycle is the rate-determining stage in the whole process and thus the precursor activation should be faster. The results obtained here help to rationalize the chemical reactivity of supported molybdenum alkylidene catalysts toward alkanes. Copyright © 2018 American Chemical Society.spa
dc.language.isoeng
dc.publisherAmerican Chemical Societyspa
dc.relation.isversionofhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85049663892&doi=10.1021%2facs.organomet.8b00090&partnerID=40&md5=e4b59b0738cd6b00550daf42f64898dfspa
dc.sourceScopusspa
dc.titleReactivity of a Silica-Supported Mo Alkylidene Catalyst toward Alkanes: A DFT Study on the Metathesis of Propanespa
dc.typeArticleeng
dc.rights.accessrightsinfo:eu-repo/semantics/restrictedAccess
dc.publisher.programCiencias Básicasspa
dc.contributor.affiliationDíaz, E., Universidad de Antioquia;Restrepo, A., Universidad de Antioquia;Núñez-Zarur, F., Universidad de Medellínspa
dc.identifier.doi10.1021/acs.organomet.8b00090
dc.relation.citationvolume37
dc.relation.citationissue13
dc.relation.citationstartpage2023
dc.relation.citationendpage2036
dc.publisher.facultyFacultad de Ciencias Básicasspa
dc.relation.ispartofesOrganometallicsspa
dc.relation.references"Vidal, V., Theolier, A., Thivolle-Cazat, J., Basset, J.M., Metathesis of Alkanes Catalyzed by Silica-Supported Transition Metal Hydrides (1997) Science, 276, pp. 99-102;Basset, J.M., Copéret, C., Soulivong, D., Taoufik, M., Cazat, J.T., Metathesis of Alkanes and Related Reactions (2010) Acc. Chem. Res., 43, pp. 323-334;Copéret, C., C-H Bond Activation and Organometallic Intermediates on Isolated Metal Centers on Oxide Surfaces (2010) Chem. Rev., 110, pp. 656-680;Rascon, F., Copéret, C., Alkylidene and Alkylidyne Surface Complexes: Precursors and Intermediates in Alkane Conversion Processes on Supported Single-Site Catalysts (2011) J. Organomet. Chem., 696, pp. 4121-4131;Pelletier, J.D.A., Basset, J.M., Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts (2016) Acc. Chem. Res., 49, pp. 664-677;Szeto, K.C., Hardou, L., Merle, N., Basset, J.M., Thivolle-Cazat, J., Papaioannou, C., Taoufik, M., Selective Conversion of Butane into Liquid Hydrocarbon Fuels on Alkane Metathesis Catalysts (2012) Catal. Sci. Technol., 2, pp. 1336-1339;Banks, R.L., Bailey, G.C., Olefin Disproportionation. A New Catalytic Process (1964) Ind. Eng. Chem. Prod. Res. Dev., 3, pp. 170-173;Jean-Louis Hérisson, P., Chauvin, Y., Catalyse de Transformation des Oléfines par les Complexes du Tungstène. II. Télomérisation des Oléfines Cycliques en Présence D'oléfines Acycliques (1971) Makromol. Chem., 141, pp. 161-176;Burnett, R.L., Hughes, T.E., Mechanism and Poisoning of the Molecular Redistribution Reaction of Alkanes with a Dual-functional Catalyst System (1973) J. Catal., 31, pp. 55-64;Goldman, A.S., Roy, A.H., Huang, Z., Ahuja, R., Schinski, W., Brookhart, M., Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation Olefin Metathesis (2006) Science, 312, pp. 257-261;Bailey, B.C., Schrock, R.R., Kundu, S., Goldman, A.S., Huang, Z., Brookhart, M., Evaluation of Molybdenum and Tungsten Metathesis Catalysts for Homogeneous Tandem Alkane Metathesis (2009) Organometallics, 28, pp. 355-360;Samantaray, M.K., Kavitake, S., Morlanes, N., Abou-Hamad, E., Hamieh, A., Dey, R., Basset, J.M., Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane (2017) J. Am. Chem. Soc., 139, pp. 3522-3527;Samantaray, M.K., Dey, R., Kavitake, S., Abou-Hamad, E., Bendjeriou-Sedjerari, A., Hamieh, A., Basset, J.M., Synergy between Two Metal Catalysts: A Highly Active Silica-Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane (2016) J. Am. Chem. Soc., 138, pp. 8595-8602;Basset, J.M., Copéret, C., Lefort, L., Maunders, B.M., Maury, O., Le Roux, E., Saggio, G., Thivolle-Cazat, J., Primary Products and Mechanistic Considerations in Alkane Metathesis (2005) J. Am. Chem. Soc., 127, pp. 8604-8605;Maury, O., Lefort, L., Vidal, V., Thivolle-Cazat, J., Basset, J.M., Metathesis of Alkanes: Evidence for Degenerate Metathesis of Ethane over a Silica-Supported Tantalum Hydride Prepared by Surface Organometallic Chemistry (1999) Angew. Chem., Int. Ed., 38, pp. 1952-1955;Chen, Y., Abou-Hamad, E., Hamieh, A., Hamzaoui, B., Emsley, L., Basset, J.M., Alkane Metathesis with the Tantalum Methylidene [(SiO)Ta(=CH2)Me-2]/[(SiO)(2)Ta(=CH2)Me] Generated from Well-Defined Surface Organometallic Complex [(SiO)(TaMe4)-Me-V] (2015) J. Am. Chem. Soc., 137, pp. 588-591;Lefort, L., Copéret, C., Taoufik, M., Thivolle-Cazat, J., Basset, J.M., H/D Exchange between CH4 and CD4 Catalysed by a Silica-Supported Tantalum Hydride, (SiO)(2)Ta-H (2000) Chem. Commun., pp. 663-664;Copéret, C., Maury, O., Thivolle-Cazat, J., Basset, J.M., Sigma-bond metathesis of alkanes on a silica-supported tantalum(v) alkyl alkylidene complex: First evidence for alkane cross-metathesis (2001) Angew. Chem., Int. Ed., 40, pp. 2331-2334;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)(3)Ta-(III) (2002) Organometallics, 21, pp. 5167-5171;Le Roux, E., Chabanas, M., Baudouin, A., De Mallmann, A., Copéret, C., Quadrelli, E.A., Thivolle-Cazat, J., Sunley, G.J., Detailed Structural Investigation of the Grafting of [Ta(=CHtBu)(CH(2)tBu)(3)] and [Cp;TaMe4] on Silica Partially Dehydroxylated at 700 Degrees C and the Activity of the Grafted Complexes Toward Alkane Metathesis (2004) J. Am. Chem. Soc., 126, pp. 13391-13399;Taoufik, M., Schwab, E., Schultz, M., Vanoppen, D., Walter, M., Thivolle-Cazat, J., Basset, J.M., Cross-metathesis between Ethane and Toluene Catalyzed by [(SiO)(2)TaH]: The First Example of a Cross-Metathesis Reaction between an Alkane and an Aromatic (2004) Chem. Commun., pp. 1434-1435;Soulivong, D., Copéret, C., Thivolle-Cazat, J., Basset, J.M., Maunders, B.M., Pardy, R.B.A., Sunley, G.J., Cross-metathesis of Propane and Methane: A Catalytic Reaction of C-C Bond Cleavage of a Higher Alkane by Methane (2004) Angew. Chem., Int. Ed., 43, pp. 5366-5369;Le Roux, E., Taoufik, M., Chabanas, M., Alcor, D., Baudouin, A., Copéret, C., Thivolle-Cazat, J., Emsley, L., Well-defined Surface Tungstenocarbyne Complexes Through the Reaction of [W(CtBu)(CH2tBu)3] with Silica (2005) Organometallics, 24, pp. 4274-4279;Taoufik, M., Le Roux, E., Thivolle-Cazat, J., Copéret, C., Basset, J.M., Maunders, B., Sunley, G.J., Alumina Supported Tungsten Hydrides, New Efficient Catalysts for Alkane Metathesis (2006) Top. Catal., 40, pp. 65-70;Le Roux, E., Taoufik, M., Baudouin, A., Copéret, C., Thivolle-Cazat, J., Basset, J.M., Maunders, B.M., Sunley, G.J., Silica-alumina-supported, Tungsten-based Heterogeneous Alkane Metathesis Catalyst: Is it Closer to a Silica- or an Alumina-Supported System? (2007) Adv. Synth. Catal., 349, pp. 231-237;Samantaray, M.K., Callens, E., Abou-Hamad, E., Rossini, A.J., Widdifield, C.M., Dey, R., Emsley, L., Basset, J.M., WMe6 Tamed by Silica: Si-O-WMe5 as an Efficient, Well-Defined Species for Alkane Metathesis, Leading to the Observation of a Supported W-Methyl/Methylidyne Species (2014) J. Am. Chem. Soc., 136, pp. 1054-1061;Hamieh, A., Chen, Y., Abdel-Azeim, S., Abou-Hamad, E., Goh, S., Samantaray, M., Dey, R., Basset, J.M., Well-Defined Surface Species [(Si-O)W(=O)Me-3) Prepared by Direct Methylation of [(Si-O-)W(=O)Cl-3), a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene (2015) ACS Catal., 5, pp. 2164-2171;Blanc, F., Coperet, C., Thivolle-Cazat, J., Basset, J.M., Alkane Metathesis Catalyzed by a Well-defined Silica-Supported Mo Imido Alkylidene Complex: [(SiO)Mo(=NAr)( =CHtBu)(CH(2)tBu)] (2006) Angew. Chem., Int. Ed., 45, pp. 6201-6203;Blanc, F., Thivolle-Cazat, J., Basset, J.M., Coperet, C., Structure-Reactivity Relationship in Alkane Metathesis Using Well-defined Silica-Supported Alkene Metathesis Catalyst Precursors (2008) Chem. - Eur. J., 14, pp. 9030-9037;Chabanas, M., Baudouin, A., Copéret, C., Basset, J.M., A Highly Active Well-defined Rhenium Heterogeneous Catalyst for Olefin Metathesis Prepared via Surface Organometallic Chemistry (2001) J. Am. Chem. Soc., 123, pp. 2062-2063;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 Two-dimensional Solid-state NMR Spectroscopy (2002) Angew. Chem., Int. Ed., 41, pp. 4535-4538;Chabanas, M., Coperet, C., Basset, J.M., Re-based Heterogeneous Catalysts for Olefin Metathesis Prepared by Surface Organometallic Chemistry: Reactivity and Selectivity (2003) Chem. - Eur. J., 9, pp. 971-975;Chabanas, M., Baudouin, A., Copéret, C., Basset, J.M., Lukens, W., Lesage, A., Hediger, S., Emsley, L., Perhydrocarbyl Re-VII Complexes: Comparison of Molecular and Surface Complexes (2003) J. Am. Chem. Soc., 125, pp. 492-504;Vidal, V., Théolier, A., Thivolle-Cazat, J., Basset, J.-M., Corker, J., Synthesis, Characterization, and Reactivity, in the C-H Bond Activation of Cycloalkanes, of a Silica-Supported Tantalum(III) Monohydride Complex (SiO)2TaIII-H (1996) J. Am. Chem. Soc., 118, pp. 4595-4602;Soignier, S., Taoufik, M., Le Roux, E., Saggio, G., Dablemont, C., Baudouin, A., Lefebvre, F., Maunders, B.M., Tantalum Hydrides Supported on MCM-41 Mesoporous Silica: Activation of Methane and Thermal Evolution of the Tantalum-Methyl Species (2006) Organometallics, 25, pp. 1569-1577;Saggio, G., Taoufik, M., Basset, J.M., Thivolle-Cazat, J., Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis (2010) ChemCatChem, 2, pp. 1594-1598;Maury, O., Lefort, L., Vidal, V., Thivolle-Cazat, J., Basset, J.M., Revisiting the Metathesis of C-13-Monolabeled Ethane (2010) Organometallics, 29, pp. 6612-6614;Le Roux, E., Taoufik, M., Copéret, 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 Structure-Activity Relationship (2005) Angew. Chem., Int. Ed., 44, pp. 6755-6758;Joubert, J., Delbecq, F., Sautet, P., Alkane Metathesis by a Tungsten Carbyne Complex Grafted on Gamma Alumina: Is There a Direct Chemical Role of the Support? (2007) J. Catal., 251, pp. 507-513;Sautet, P., Delbecq, F., Catalysis and Surface Organometallic Chemistry: A View from Theory and Simulations (2010) Chem. Rev., 110, pp. 1788-1806;Schinzel, S., Chermette, H., Coperet, C., Basset, J.M., Evaluation of the Carbene Hydride Mechanism in the Carbon-Carbon Bond Formation Process of Alkane Metathesis Through a DFT Study (2008) J. Am. Chem. Soc., 130, pp. 7984-7987;Mazar, M.N., Al-Hashimi, S., Bhan, A., Cococcioni, M., Alkane Metathesis by Tantalum Metal Hydride on Ferrierite: A Computational Study (2011) J. Phys. Chem. C, 115, pp. 10087-10096;Núñez-Zarur, F., Solans-Monfort, X., Restrepo, A., Mechanistic Insights into Alkane Metathesis Catalyzed by Silica-Supported Tantalum Hydrides: A DFT Study (2017) Inorg. Chem., 56, pp. 10458-10473;Blanc, F., Copéret, 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)] (2006) Angew. Chem., Int. Ed., 45, pp. 1216-1220;Poater, A., Solans-Monfort, X., Clot, E., Coperet, C., Eisenstein, O., DFT Calculations of d0M(NR)(CHtBu)(X)(Y) (M = Mo, W;R = CPh3, 2,6-iPr-C6H3;X and y = CH2tBu, OtBu, OSi(OtBu)3) Olefin Metathesis Catalysts: Structural, Spectroscopic and Electronic Properties (2006) Dalton Trans., pp. 3077-3087;Chabanas, M., Vidal, V., Copéret, C., Thivolle-Cazat, J., Basset, J.M., Low-temperature Hydrogenolysis of Alkanes Catalyzed by a Silica-Supported Tantalum Hydride Complex, and Evidence for a Mechanistic Switch from Group IV to Group v Metal Surface Hydride Complexes (2000) Angew. Chem., Int. Ed., 39, pp. 1962-1965;Polshettiwar, V., Pasha, F.A., De Mallmann, A., Norsic, S., Thivolle-Cazat, J., Basset, J.M., Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study (2012) ChemCatChem, 4, pp. 363-369;Pasha, F.A., Cavallo, L., Basset, J.M., Mechanism of n-Butane Hydrogenolysis Promoted by Ta-Hydrides Supported on Silica (2014) ACS Catal., 4, pp. 1868-1874;Solans-Monfort, X., Copéret, C., Eisenstein, O., Shutting Down Secondary Reaction Pathways: The Essential Role of the Pyrrolyl Ligand in Improving Silica Supported d(0)-ML4 Alkene Metathesis Catalysts from DFT Calculations (2010) J. Am. Chem. Soc., 132, pp. 7750-7757;Leduc, A.M., Salameh, A., Soulivong, D., Chabanas, M., Basset, J.M., Copéret, C., Solans-Monfort, X., Roper, M., Beta-H Transfer from the Metallacyclobutane: A key step in the Deactivation and Byproduct Formation for the Well-defined Silica-Supported Rhenium Alkylidene Alkene Metathesis Catalyst (2008) J. Am. Chem. Soc., 130, pp. 6288-6297;Solans-Monfort, X., Filhol, J.-S., Coperet, C., Eisenstein, O., Structure, Spectroscopic and Electronic Properties of a Well Defined Silica Supported Olefin Metathesis Catalyst, [(SiO)Re(CR)(CHR)(CH2R)], Through DFT Periodic Calculations: Silica is Just a Large Siloxy Ligand (2006) New J. Chem., 30, pp. 842-850;Blanc, F., Basset, J.-M., Copéret, C., Sinha, A., Tonzetich, Z.J., Schrock, R.R., Solans-Monfort, X., Emsley, L., Dynamics of Silica-Supported Catalysts Determined by Combining Solid-State NMR Spectroscopy and DFT Calculations (2008) J. Am. Chem. Soc., 130, pp. 5886-5900;Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Fox, D.J., (2009) Gaussian 09, Revision D.01, , Gaussian, Inc. Wallingford, CT;Perdew, J.P., Wang, Y., Accurate and Simple Analytic Representation of the Electron-Gas Correlation Energy (1992) Phys. Rev. B: Condens. Matter Mater. Phys., 45, pp. 13244-13249;Becke, A.D., Density-Functional Thermochemistry 0.3. the Role of Exact Exchange (1993) J. Chem. Phys., 98, pp. 5648-5652;Andrae, D., Häußermann, U., Dolg, M., Stoll, H., Preuß, H., Energy-adjusted Ab Initio Pseudopotentials for the Second and Third Row Transition Elements (1990) Theor. Chim. Acta, 77, pp. 123-141;Bergner, A., Dolg, M., Küchle, W., Stoll, H., Preuß, H., Ab Initio Energy-adjusted Pseudopotentials for Elements of Groups 13-17 (1993) Mol. Phys., 80, pp. 1431-1441;Ehlers, A.W., Bohme, M., Dapprich, S., Gobbi, A., Hollwarth, A., Jonas, V., Kohler, K.F., Frenking, G., A Set of F-Polarization Functions for Pseudo-Potential Basis-Sets of the Transition-Metals Sc-Cu, Y-Ag and La-Au (1993) Chem. Phys. Lett., 208, pp. 111-114;Höllwarth, A., Böhme, M., Dapprich, S., Ehlers, A.W., Gobbi, A., Jonas, V., Köhler, K.F., Frenking, G., A Set of d-polarization Functions for Pseudopotential Basis Sets of the Main Group Elements Al-Bi and f-type Polarization Functions for Zn, Cd, Hg (1993) Chem. Phys. Lett., 208, pp. 237-240;Hehre, W.J., Ditchfield, R., Pople, J.A., Self-Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian-Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules (1972) J. Chem. Phys., 56, pp. 2257-2261;Hariharan, P.C., Pople, J.A., The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies (1973) Theor. Chim. Acta, 28, pp. 213-222;Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., Self-Consistent Molecular-Orbital Methods. 20. Basis Set for Correlated Wave-Functions (1980) J. Chem. Phys., 72, pp. 650-654;Frisch, M.J., Pople, J.A., Binkley, J.S., Self-Consistent Molecular-Orbital Methods. 25. Supplementary Functions for Gaussian-Basis Sets (1984) J. Chem. Phys., 80, pp. 3265-3269;Waterman, R., ?-Bond Metathesis: A 30-Year Retrospective (2013) Organometallics, 32, pp. 7249-7263;Balcells, D., Clot, E., Eisenstein, O., C-H Bond Activation in Transition Metal Species from a Computational Perspective (2010) Chem. Rev., 110, pp. 749-823;Solans-Monfort, X., Clot, E., Copéret, C., Eisenstein, O., D0 Re-Based Olefin Metathesis Catalysts, Re(CR)(CHR)(X)(Y): The Key Role of X and y Ligands for Efficient Active Sites (2005) J. Am. Chem. Soc., 127, pp. 14015-14025;Poater, A., Solans-Monfort, X., Clot, E., Copéret, C., Eisenstein, O., Understanding d0-Olefin Metathesis Catalysts: Which Metal, Which Ligands? (2007) J. Am. Chem. Soc., 129, pp. 8207-8216;Solans-Monfort, X., Copéret, C., Eisenstein, O., Metallacyclobutanes from Schrock-Type d0Metal Alkylidene Catalysts: Structural Preferences and Consequences in Alkene Metathesis (2015) Organometallics, 34, pp. 1668-1680;Wallace, K.C., Dewan, J.C., Schrock, R.R., Multiple Metal-Carbon Bonds. 44. Isolation and Characterization of the First Simple Tantalacyclobutane Complexes (1986) Organometallics, 5, pp. 2162-2164;Schrock, R.R., Depue, R.T., Feldman, J., Schaverien, C.J., Dewan, J.C., Liu, A.H., Preparation and Reactivity of Several Alkylidene Complexes of the Type W(CHR')(N-2,6-C6H3-iso-Pr2)(OR)2 and Related Tungstacyclobutane Complexes. Controlling Metathesis Activity Through the Choice of Alkoxide Ligand (1988) J. Am. Chem. Soc., 110, pp. 1423-1435;Wallace, K.C., Liu, A.H., Dewan, J.C., Schrock, R.R., Preparation and Reactions of Tantalum Alkylidene Complexes Containing Bulky Phenoxide or Thiolate Ligands. Controlling Ring-opening Metathesis Polymerization Activity and Mechanism Through Choice of Anionic Ligand (1988) J. Am. Chem. Soc., 110, pp. 4964-4977;Feldman, J., Davis, W.M., Schrock, R.R., Trigonal-bipyramidal and Square-pyramidal Tungstacyclobutane Intermediates are Both Present in Systems in Which Olefins are Metathesized by Complexes of the Type W(CHR')(N-2,6-C6H3-iso-Pr2)(OR)2 (1989) Organometallics, 8, pp. 2266-2268;Jiang, A.J., Simpson, J.H., Müller, P., Schrock, R.R., Fundamental Studies of Tungsten Alkylidene Imido Monoalkoxidepyrrolide Complexes (2009) J. Am. Chem. Soc., 131, pp. 7770-7780;Schrock, R.R., Jiang, A.J., Marinescu, S.C., Simpson, J.H., Müller, P., Fundamental Studies of Molybdenum and Tungsten Methylidene and Metallacyclobutane Complexes (2010) Organometallics, 29, pp. 5241-5251;Peryshkov, D.V., Schrock, R.R., Takase, M.K., Müller, P., Hoveyda, A.H., Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes (2011) J. Am. Chem. Soc., 133, pp. 20754-20757;Reithofer, M.R., Dobereiner, G.E., Schrock, R.R., Müller, P., Monoaryloxide Pyrrolide (MAP) Imido Alkylidene Complexes of Molybdenum and Tungsten That Contain 2,6-Bis(2,5-R2-pyrrolyl)phenoxide (R = i-Pr, Ph) Ligands and an Unsubstituted Metallacyclobutane on Its Way to Losing Ethylene (2013) Organometallics, 32, pp. 2489-2492;Schrock, R.R., Depue, R.T., Feldman, J., Yap, K.B., Yang, D.C., Davis, W.M., Park, L., Schofield, M., Further Studies of Imido Alkylidene Complexes of Tungsten, Well-characterized Olefin Metathesis Catalysts with Controllable Activity (1990) Organometallics, 9, pp. 2262-2275;Feldman, J., Davis, W.M., Thomas, J.K., Schrock, R.R., Preparation and Reactivity of Tungsten(VI) Metallacyclobutane Complexes. Square Pyramids versus Trigonal Bipyramids (1990) Organometallics, 9, pp. 2535-2548;Vaughan, G.A., Toreki, R., Schrock, R.R., Davis, W.M., Reversible ""3 + 2 Cycloaddition"" of Ethylene to the CReC Unit in Rhenium Complexes of the Type Re(CtBu3)(CHR')(OR)2 (1993) J. Am. Chem. Soc., 115, pp. 2980-2981;Blanc, F., Berthoud, R., Copéret, 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 (2008) Proc. Natl. Acad. Sci. U. S. A., 105, p. 12123;Mougel, V., Coperet, C., Magnitude and Consequences of or Ligand Sigma-donation on Alkene Metathesis Activity in d(0) Silica Supported (SiO)W(NAr)( =CHtBu)(OR) Catalysts (2014) Chem. Sci., 5, pp. 2475-2481;Conley, M.P., Forrest, W.P., Mougel, V., Copéret, C., Schrock, R.R., Bulky Aryloxide Ligand Stabilizes a Heterogeneous Metathesis Catalyst (2014) Angew. Chem., Int. Ed., 53, pp. 14221-14224;Allouche, F., Mougel, V., Copéret, C., Activating Thiolate-Based Imidoalkylidene Tungsten(VI) Metathesis Catalysts by Grafting onto Silica (2015) Asian J. Org. Chem., 4, pp. 528-532;Mougel, V., Santiago, C.B., Zhizhko, P.A., Bess, E.N., Varga, J., Frater, G., Sigman, M.S., Copéret, C., Quantitatively Analyzing Metathesis Catalyst Activity and Structural Features in Silica-Supported Tungsten Imido-Alkylidene Complexes (2015) J. Am. Chem. Soc., 137, pp. 6699-6704;Mougel, V., Pucino, M., Copéret, C., Strongly ? Donating Thiophenoxide in Silica-Supported Tungsten Oxo Catalysts for Improved 1-Alkene Metathesis Efficiency (2015) Organometallics, 34, pp. 551-554;Ong, T.-C., Liao, W.-C., Mougel, V., Gajan, D., Lesage, A., Emsley, L., Copéret, C., Atomistic Description of Reaction Intermediates for Supported Metathesis Catalysts Enabled by DNP SENS (2016) Angew. Chem., Int. Ed., 55, pp. 4743-4747;Mougel, V., Chan, K.-W., Siddiqi, G., Kawakita, K., Nagae, H., Tsurugi, H., Mashima, K., Copéret, C., Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents (2016) ACS Cent. Sci., 2, pp. 569-576;Valla, M., Wischert, R., Comas-Vives, A., Conley, M.P., Verel, R., Copéret, C., Sautet, P., Role of Tricoordinate Al Sites in CH3ReO3/Al2O3 Olefin Metathesis Catalysts (2016) J. Am. Chem. Soc., 138, pp. 6774-6785;Solans-Monfort, X., Copéret, C., Eisenstein, O., Oxo vs Imido Alkylidene d0-Metal Species: How and Why Do They Differ in Structure, Activity, and Efficiency in Alkene Metathesis? (2012) Organometallics, 31, pp. 6812-6822;Kozuch, S., Shaik, S., A Combined Kinetic-quantum Mechanical Model for Assessment of Catalytic Cycles: Application to Cross-coupling and Heck Reactions (2006) J. Am. Chem. Soc., 128, pp. 3355-3365;Kozuch, S., Lee, S.E., Shaik, S., Theoretical Analysis of the Catalytic Cycle of a Nickel Cross-Coupling Process: Application of the Energetic Span Model (2009) Organometallics, 28, pp. 1303-1308;Uhe, A., Kozuch, S., Shaik, S., Automatic Analysis of Computed Catalytic Cycles (2011) J. Comput. Chem., 32, pp. 978-985;Kozuch, S., Shaik, S., How to Conceptualize Catalytic Cycles? the Energetic Span Model (2011) Acc. Chem. Res., 44, pp. 101-110;Kozuch, S., Shaik, S., Kinetic-quantum Chemical Model for Catalytic Cycles: The Haber-Bosch Process and the Effect of Reagent Concentration (2008) J. Phys. Chem. A, 112, pp. 6032-6041;Brogaard, R.Y., Olsbye, U., Ethene Oligomerization in Ni-Containing Zeolites: Theoretical Discrimination of Reaction Mechanisms (2016) ACS Catal., 6, pp. 1205-1214;Bailey, B.C., Fan, H., Baum, E.W., Huffman, J.C., Baik, M.-H., Mindiola, D.J., Intermolecular C-H Bond Activation Promoted by a Titanium Alkylidyne (2005) J. Am. Chem. Soc., 127, pp. 16016-16017;Bailey, B.C., Fan, H.J., Huffman, J.C., Baik, M.H., Mindiola, D.J., Intermolecular C-H Bond Activation Reactions Promoted by Transient Titanium Alkylidynes. Synthesis, Reactivity, Kinetic, and Theoretical Studies of the Ti C Linkage (2007) J. Am. Chem. Soc., 129, pp. 8781-8793;Bailey, B.C., Fout, A.R., Fan, H., Tomaszewski, J., Huffman, J.C., Mindiola, D.J., An Alkylidyne Analogue of Tebbe's Reagent: Trapping Reactions of a Titanium Neopentylidyne by Incomplete and Complete 1,2-Additions (2007) Angew. Chem., Int. Ed., 46, pp. 8246-8249;Fout, A.R., Scott, J., Miller, D.L., Bailey, B.C., Pink, M., Mindiola, D.J., Dehydrofluorination of Hydrofluorocarbons by Titanium Alkylidynes via Sequential C-H/C-F Bond Activation Reactions. A Synthetic, Structural, and Mechanistic Study of 1,2-CH Bond Addition and ?-Fluoride Elimination (2009) Organometallics, 28, pp. 331-347;Kamitani, M., Pinter, B., Searles, K., Crestani, M.G., Hickey, A., Manor, B.C., Carroll, P.J., Mindiola, D.J., Phosphinoalkylidene and -alkylidyne Complexes of Titanium: Intermolecular C-H Bond Activation and Dehydrogenation Reactions (2015) J. Am. Chem. Soc., 137, pp. 11872-11875;Riache, N., Callens, E., Samantaray, M.K., Kharbatia, N.M., Atiqullah, M., Basset, J.M., Cyclooctane Metathesis Catalyzed by Silica-Supported Tungsten Pentamethyl [(SiO)W(Me)(5)]: Distribution of Macrocyclic Alkanes (2014) Chem. - Eur. J., 20, pp. 15089-15094"spa
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