Literature DB >> 18723685

Direct observation of reaction intermediates for a well defined heterogeneous alkene metathesis catalyst.

Frédéric Blanc1, Romain Berthoud, Christophe Copéret, Anne Lesage, Lyndon Emsley, Rojendra Singh, Thorsten Kreickmann, Richard R Schrock.   

Abstract

Grafting of [W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))(2)] on a silica partially dehydroxylated at 700 degrees C (SiO(2- (700))) generates the corresponding monosiloxy complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))] as the major species (approximately 90%) along with [([triple bond]SiO)W([triple bond]NAr)(CH(2)tBu)(2,5-Me(2)NC(4)H(2))(2)], according to mass balance analysis, IR, and NMR studies. This heterogeneous catalyst displays good activity and stability in the metathesis of propene. Very importantly, solid state NMR spectroscopy allows observation of the propagating alkylidene as well as stable metallacyclobutane intermediates. These species have the same reactivity as the initial surface complex [([triple bond]SiO)W([triple bond]NAr)(=CHtBu)(2,5-Me(2)NC(4)H(2))], which shows that they are the key intermediates of alkene metathesis.

Entities:  

Year:  2008        PMID: 18723685      PMCID: PMC2527876          DOI: 10.1073/pnas.0802147105

Source DB:  PubMed          Journal:  Proc Natl Acad Sci U S A        ISSN: 0027-8424            Impact factor:   11.205


  23 in total

1.  A highly active well-defined rhenium heterogeneous catalyst for olefin metathesis prepared via surface organometallic chemistry.

Authors:  M Chabanas; A Baudouin; C Copéret; J M Basset
Journal:  J Am Chem Soc       Date:  2001-03-07       Impact factor: 15.419

2.  Olefin-metathesis catalysts for the preparation of molecules and materials (Nobel Lecture).

Authors:  Robert H Grubbs
Journal:  Angew Chem Int Ed Engl       Date:  2006-06-02       Impact factor: 15.336

3.  Design and understanding of heterogeneous alkene metathesis catalysts.

Authors:  Christophe Copéret
Journal:  Dalton Trans       Date:  2007-11-05       Impact factor: 4.390

4.  Dramatic improvements of well-defined silica supported Mo-based olefin metathesis catalysts by tuning the N-containing ligands.

Authors:  Frédéric Blanc; Romain Berthoud; Alain Salameh; Jean-Marie Basset; Christophe Copéret; Rojendra Singh; Richard R Schrock
Journal:  J Am Chem Soc       Date:  2007-06-16       Impact factor: 15.419

5.  Understanding d(0)-olefin metathesis catalysts: which metal, which ligands?

Authors:  Albert Poater; Xavier Solans-Monfort; Eric Clot; Christophe Copéret; Odile Eisenstein
Journal:  J Am Chem Soc       Date:  2007-06-09       Impact factor: 15.419

6.  Direct observation of a 14-electron ruthenacyclobutane relevant to olefin metathesis.

Authors:  Patricio E Romero; Warren E Piers
Journal:  J Am Chem Soc       Date:  2005-04-13       Impact factor: 15.419

7.  d0 Re-based olefin metathesis catalysts, Re([triple bond]CR)(=CHR)(X)(Y): the key role of X and Y ligands for efficient active sites.

Authors:  Xavier Solans-Monfort; Eric Clot; Christophe Copéret; Odile Eisenstein
Journal:  J Am Chem Soc       Date:  2005-10-12       Impact factor: 15.419

8.  Ruthenium metallacycles derived from 14-electron complexes. New insights into olefin metathesis intermediates.

Authors:  Anna G Wenzel; Robert H Grubbs
Journal:  J Am Chem Soc       Date:  2006-12-20       Impact factor: 15.419

9.  Alkylidene and metalacyclic complexes of tungsten that contain a chiral biphenoxide ligand. synthesis, asymmetric ring-closing metathesis, and mechanistic investigations.

Authors:  W C Peter Tsang; Kai C Hultzsch; John B Alexander; Peter J Bonitatebus; Richard R Schrock; Amir H Hoveyda
Journal:  J Am Chem Soc       Date:  2003-03-05       Impact factor: 15.419

10.  Dissociation of acetaldehyde on beta-Mo2C to yield ethylidene and oxo surface groups: a possible pathway for active site formation in heterogeneous olefin metathesis.

Authors:  Mohamed Siaj; Corey Reed; S Ted Oyama; Susannah L Scott; Peter H McBreen
Journal:  J Am Chem Soc       Date:  2004-08-11       Impact factor: 15.419

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  7 in total

1.  Characterization and dynamics of substituted ruthenacyclobutanes relevant to the olefin cross-metathesis reaction.

Authors:  Anna G Wenzel; Garrett Blake; David G VanderVelde; Robert H Grubbs
Journal:  J Am Chem Soc       Date:  2011-03-31       Impact factor: 15.419

Review 2.  Recent advances in high oxidation state Mo and W imido alkylidene chemistry.

Authors:  Richard R Schrock
Journal:  Chem Rev       Date:  2009-08       Impact factor: 60.622

3.  Stereoselectivity of supported alkene metathesis catalysts: a goal and a tool to characterize active sites.

Authors:  Christophe Copéret
Journal:  Beilstein J Org Chem       Date:  2011-01-05       Impact factor: 2.883

4.  Three-Dimensional Structure Determination of Surface Sites.

Authors:  Pierrick Berruyer; Moreno Lelli; Matthew P Conley; Daniel L Silverio; Cory M Widdifield; Georges Siddiqi; David Gajan; Anne Lesage; Christophe Copéret; Lyndon Emsley
Journal:  J Am Chem Soc       Date:  2017-01-05       Impact factor: 15.419

5.  Metathesis Activity Encoded in the Metallacyclobutane Carbon-13 NMR Chemical Shift Tensors.

Authors:  Christopher P Gordon; Keishi Yamamoto; Wei-Chih Liao; Florian Allouche; Richard A Andersen; Christophe Copéret; Christophe Raynaud; Odile Eisenstein
Journal:  ACS Cent Sci       Date:  2017-06-14       Impact factor: 14.553

6.  Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents.

Authors:  Victor Mougel; Ka-Wing Chan; Georges Siddiqi; Kento Kawakita; Haruki Nagae; Hayato Tsurugi; Kazushi Mashima; Olga Safonova; Christophe Copéret
Journal:  ACS Cent Sci       Date:  2016-08-04       Impact factor: 14.553

7.  Direct structural identification of carbenium ions and investigation of host-guest interaction in the methanol to olefins reaction obtained by multinuclear NMR correlations.

Authors:  Dong Xiao; Shutao Xu; Xiuwen Han; Xinhe Bao; Zhongmin Liu; Frédéric Blanc
Journal:  Chem Sci       Date:  2017-10-10       Impact factor: 9.825

  7 in total

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