DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes

Abstract

In this work, new tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by single-crystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1-phenyl-1-propyne. Overall, incorporation of bidentate and strongly $$σ$$ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [4];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Stuttgart (Germany). Inst. of Polymer Chemistry
  2. Univ. of Stuttgart (Germany). Inst. of Organic Chemistry
  3. Univ. of Innsbruck (Austria). Inst. of General, Inorganic and Theoretical Chemistry
  4. Univ. of Stuttgart (Germany). Inst. for Theoretical Chemistry
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); German Research Foundation (DFG)
OSTI Identifier:
1598275
Grant/Contract Number:  
AC02-76SF00515; 358283783-CRC 1333
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 38; Journal Issue: 21; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemical structure; Metals; Ligands; Particulate matter; Crystal structure

Citation Formats

Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, and Buchmeiser, Michael R.. Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes. United States: N. p., 2019. Web. doi:10.1021/acs.organomet.9b00481.
Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, & Buchmeiser, Michael R.. Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes. United States. https://doi.org/10.1021/acs.organomet.9b00481
Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, and Buchmeiser, Michael R.. Fri . "Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes". United States. https://doi.org/10.1021/acs.organomet.9b00481. https://www.osti.gov/servlets/purl/1598275.
@article{osti_1598275,
title = {Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes},
author = {Elser, Iris and Groos, Jonas and Hauser, Philipp M. and Koy, Maximilian and van der Ende, Melita and Wang, Dongren and Frey, Wolfgang and Wurst, Klaus and Meisner, Jan and Ziegler, Felix and Kästner, Johannes and Buchmeiser, Michael R.},
abstractNote = {In this work, new tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by single-crystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1-phenyl-1-propyne. Overall, incorporation of bidentate and strongly $σ$ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.},
doi = {10.1021/acs.organomet.9b00481},
journal = {Organometallics},
number = 21,
volume = 38,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Well-defined alkyne metathesis catalysts developed in the groups of Mortreux,6 Schrock,3a - i Cummins,7 Fiirstner,4a - d Moore,8 Tammsb- e and Buchmeiser.12

Save / Share:

Works referenced in this record:

A Highly Active, Heterogeneous Catalyst for Alkyne Metathesis
journal, January 2006

  • Weissman, Haim; Plunkett, Kyle N.; Moore, Jeffrey S.
  • Angewandte Chemie International Edition, Vol. 45, Issue 4
  • DOI: 10.1002/anie.200502840

Alkyne metathesis
journal, January 2005

  • Fürstner, Alois; Davies, Paul W.
  • Chemical Communications, Issue 18
  • DOI: 10.1039/b419143a

Abnormal binding in a carbene complex formed from an imidazolium salt and a metal hydride complex
journal, January 2001

  • Gründemann, Stephan; Kovacevic, Anes; Albrecht, Martin
  • Chemical Communications, Issue 21
  • DOI: 10.1039/b107881j

High-oxidation-state molybdenum and tungsten alkylidyne complexes
journal, November 1986

  • Schrock, Richard R.
  • Accounts of Chemical Research, Vol. 19, Issue 11
  • DOI: 10.1021/ar00131a003

Metathesis vs. Polymerization of terminal acetylenes over [W(CBut)(OBut)3]
journal, January 1993

  • Bray, Alvar; Mortreux, Andr�; Petit, Francis
  • Journal of the Chemical Society, Chemical Communications, Issue 2
  • DOI: 10.1039/c39930000197

Normal-to-Abnormal Rearrangement and NHC Activation in Three-Coordinate Iron(II) Carbene Complexes
journal, August 2013

  • Day, Benjamin M.; Pugh, Thomas; Hendriks, Daniël
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja408589p

The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage
journal, September 2015

  • Lackner, Aaron D.; Fürstner, Alois
  • Angewandte Chemie International Edition, Vol. 54, Issue 43
  • DOI: 10.1002/anie.201506546

Efficient Metathesis of Terminal Alkynes
journal, November 2012

  • Haberlag, Birte; Freytag, Matthias; Daniliuc, Constantin G.
  • Angewandte Chemie International Edition, Vol. 51, Issue 52
  • DOI: 10.1002/anie.201207772

First and Second Proton Affinities of Carbon Bases
journal, July 2008

  • Tonner, Ralf; Heydenrych, Greta; Frenking, Gernot
  • ChemPhysChem, Vol. 9, Issue 10
  • DOI: 10.1002/cphc.200800208

Alkyne Metathesis with Silica-Supported and Molecular Catalysts at Parts-per-Million Loadings
journal, August 2016

  • Estes, Deven P.; Bittner, Celine; Àrias, Òscar
  • Angewandte Chemie International Edition, Vol. 55, Issue 45
  • DOI: 10.1002/anie.201605129

Preparation of Imidazolin-2-iminato Molybdenum and Tungsten Benzylidyne Complexes: A New Pathway to Highly Active Alkyne Metathesis Catalysts
journal, June 2010

  • Haberlag, Birte; Wu, Xian; Brandhorst, Kai
  • Chemistry - A European Journal, Vol. 16, Issue 29
  • DOI: 10.1002/chem.201000597

Dinitrogen Cleavage Stemming from a Heterodinuclear Niobium/Molybdenum N 2 Complex:  New Nitridoniobium Systems Including a Niobazene Cyclic Trimer
journal, March 2000

  • Mindiola, Daniel J.; Meyer, Karsten; Cherry, John-Paul F.
  • Organometallics, Vol. 19, Issue 9
  • DOI: 10.1021/om000159k

Syntheses of Molybdenum Oxo Alkylidene Complexes through Addition of Water to an Alkylidyne Complex
journal, February 2018

  • Bukhryakov, Konstantin V.; Schrock, Richard R.; Hoveyda, Amir H.
  • Journal of the American Chemical Society, Vol. 140, Issue 8
  • DOI: 10.1021/jacs.8b00499

Synthetic Applications with Use of a Silica-Supported Alkyne Metathesis Catalyst
journal, May 2008

  • Cho, Hyeon Mo; Weissman, Haim; Moore, Jeffrey S.
  • The Journal of Organic Chemistry, Vol. 73, Issue 11
  • DOI: 10.1021/jo8003919

Abnormal, mesoionic and remote N-heterocyclic carbene complexes
journal, February 2013


Optimized Synthesis, Structural Investigations, Ligand Tuning and Synthetic Evaluation of Silyloxy-Based Alkyne Metathesis Catalysts
journal, July 2012

  • Heppekausen, Johannes; Stade, Robert; Kondoh, Azusa
  • Chemistry - A European Journal, Vol. 18, Issue 33
  • DOI: 10.1002/chem.201200621

Facile Synthesis of Trialkoxymolybdenum(VI) Alkylidyne Complexes for Alkyne Metathesis
journal, December 2000

  • Tsai, Yi-Chou; Diaconescu, Paula L.; Cummins, Christopher C.
  • Organometallics, Vol. 19, Issue 25
  • DOI: 10.1021/om000644f

Correlations and Predictions of p K a Values of Fluorophenols and Bromophenols Using Hydrogen-Bonded Complexes with Ammonia
journal, January 2006

  • Han, Jun; Tao, Fu-Ming
  • The Journal of Physical Chemistry A, Vol. 110, Issue 1
  • DOI: 10.1021/jp052824e

Mo[N( t -Bu)(Ar)] 3 Complexes As Catalyst Precursors:  In Situ Activation and Application to Metathesis Reactions of Alkynes and Diynes
journal, October 1999

  • Fürstner, Alois; Mathes, Christian; Lehmann, Christian W.
  • Journal of the American Chemical Society, Vol. 121, Issue 40
  • DOI: 10.1021/ja991340r

Molybdenum and Tungsten Imido Alkylidene N-Heterocyclic Carbene Catalysts Bearing Cationic Ligands for Use in Biphasic Olefin Metathesis
journal, April 2017

  • Elser, Iris; Schowner, Roman; Frey, Wolfgang
  • Chemistry - A European Journal, Vol. 23, Issue 26
  • DOI: 10.1002/chem.201700213

Well‐Defined Alkyne Metathesis Catalysts: Developments and Recent Applications
journal, December 2018


Preparation of Cyclophanes by Room-Temperature Ring-Closing Alkyne Metathesis with Imidazolin-2-iminato Tungsten Alkylidyne Complexes
journal, February 2008

  • Beer, Stephan; Brandhorst, Kai; Grunenberg, Jörg
  • Organic Letters, Vol. 10, Issue 5
  • DOI: 10.1021/ol800154y

Dinitrogen Cleavage by Three-Coordinate Molybdenum(III) Complexes:  Mechanistic and Structural Data 1
journal, January 1996

  • Laplaza, Catalina E.; Johnson, Marc J. A.; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 118, Issue 36
  • DOI: 10.1021/ja960574x

Investigations into Ruthenium Metathesis Catalysts with Six-Membered Chelating NHC Ligands: Relationship between Catalyst Structure and Stereoselectivity
journal, August 2013

  • Endo, Koji; Herbert, Myles B.; Grubbs, Robert H.
  • Organometallics, Vol. 32, Issue 18
  • DOI: 10.1021/om4006966

Molybdenum Imido Alkylidene Complexes Containing N- and C-Chelating N-Heterocyclic Carbenes
journal, December 2016


Alkyne Metathesis on the Rise
journal, January 2013


Tungsten(VI) neopentylidyne complexes
journal, December 1982

  • Schrock, R. R.; Clark, D. N.; Sancho, J.
  • Organometallics, Vol. 1, Issue 12
  • DOI: 10.1021/om00072a018

Electronic and Steric Parameters of 76 N-Heterocyclic Carbenes in Ni(CO) 3 (NHC)
journal, October 2009


Rendering Schrock-type Molybdenum Alkylidene Complexes Air Stable: User-Friendly Precatalysts for Alkene Metathesis
journal, July 2011

  • Heppekausen, Johannes; Fürstner, Alois
  • Angewandte Chemie International Edition, Vol. 50, Issue 34, p. 7829-7832
  • DOI: 10.1002/anie.201102012

Alkyne metathesis by molybdenum and tungsten alkylidyne complexes
journal, January 2013


N-Heterocyclic Carbene, High Oxidation State Molybdenum Alkylidene Complexes: Functional-Group-Tolerant Cationic Metathesis Catalysts
journal, August 2014

  • Buchmeiser, Michael R.; Sen, Suman; Unold, Jörg
  • Angewandte Chemie International Edition, Vol. 53, Issue 35
  • DOI: 10.1002/anie.201404655

Synthesis and characterization of rhenium(VII) alkylidene alkylidyne complexes of the type Re(CR')(CHR')(OR)2 and related species
journal, April 1992

  • Toreki, Robert; Schrock, Richard R.; Davis, William M.
  • Journal of the American Chemical Society, Vol. 114, Issue 9
  • DOI: 10.1021/ja00035a031

Metathesis of alkynes by a molybdenum hexacarbonyl–resorcinol catalyst
journal, January 1974

  • Mortreux, André; Blanchard, Michel
  • J. Chem. Soc., Chem. Commun., Issue 19
  • DOI: 10.1039/C39740000786

Practical New Silyloxy-Based Alkyne Metathesis Catalysts with Optimized Activity and Selectivity Profiles
journal, August 2010

  • Heppekausen, Johannes; Stade, Robert; Goddard, Richard
  • Journal of the American Chemical Society, Vol. 132, Issue 32
  • DOI: 10.1021/ja104800w

Experimental and Theoretical Investigations of Catalytic Alkyne Cross-Metathesis with Imidazolin-2-iminato Tungsten Alkylidyne Complexes
journal, January 2009

  • Beer, Stephan; Brandhorst, Kai; Hrib, Cristian G.
  • Organometallics, Vol. 28, Issue 5
  • DOI: 10.1021/om801119t

Alkyne Metathesis: Catalysts and Synthetic Applications
journal, January 2007

  • Zhang, Wei; Moore, Jeffrey S.
  • Advanced Synthesis & Catalysis, Vol. 349, Issue 1-2
  • DOI: 10.1002/adsc.200600476

A New Class of Chelating N-Heterocyclic Carbene Ligands and Their Complexes with Palladium
journal, June 2004

  • Waltman, Andrew W.; Grubbs, Robert H.
  • Organometallics, Vol. 23, Issue 13
  • DOI: 10.1021/om049727c

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
journal, October 1984

  • Freudenberger, John H.; Schrock, Richard R.; Churchill, Melvyn Rowen
  • Organometallics, Vol. 3, Issue 10
  • DOI: 10.1021/om00088a019

Facile Synthesis of a Tungsten Alkylidyne Catalyst for Alkyne Metathesis
journal, January 2007

  • Tonzetich, Zachary J.; Lam, Yan Choi; Müller, Peter
  • Organometallics, Vol. 26, Issue 3
  • DOI: 10.1021/om0610647

Multidentate Triphenolsilane-Based Alkyne Metathesis Catalysts
journal, March 2013

  • Yang, Haishen; Liu, Zhenning; Zhang, Wei
  • Advanced Synthesis & Catalysis, Vol. 355, Issue 5
  • DOI: 10.1002/adsc.201201105

Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Structure-Productivity Correlations and Mechanistic Insights
journal, July 2016

  • Buchmeiser, Michael R.; Sen, Suman; Lienert, Christina
  • ChemCatChem, Vol. 8, Issue 16
  • DOI: 10.1002/cctc.201600624

An OCO 3– Trianionic Pincer Tungsten(VI) Alkylidyne: Rational Design of a Highly Active Alkyne Polymerization Catalyst
journal, March 2012

  • Sarkar, Soumya; McGowan, Kevin P.; Kuppuswamy, Subramaniam
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja2117975

Chelated Ruthenium Catalysts for Z -Selective Olefin Metathesis
journal, June 2011

  • Endo, Koji; Grubbs, Robert H.
  • Journal of the American Chemical Society, Vol. 133, Issue 22
  • DOI: 10.1021/ja202818v

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis
journal, November 2017

  • Estes, Deven P.; Gordon, Christopher P.; Fedorov, Alexey
  • Journal of the American Chemical Society, Vol. 139, Issue 48
  • DOI: 10.1021/jacs.7b09934

High Oxidation State Molybdenum N -Heterocyclic Carbene Alkylidyne Complexes: Synthesis, Mechanistic Studies, and Reactivity
journal, October 2017

  • Koy, Maximilian; Elser, Iris; Meisner, Jan
  • Chemistry - A European Journal, Vol. 23, Issue 61
  • DOI: 10.1002/chem.201703313

Synthesis of Ether-Functionalized and Sterically Demanding Molybdenum Alkylidyne Complexes
journal, December 2018


Highly Active Trialkoxymolybdenum(VI) Alkylidyne Catalysts Synthesized by a Reductive Recycle Strategy
journal, January 2004

  • Zhang, Wei; Kraft, Stefan; Moore, Jeffrey S.
  • Journal of the American Chemical Society, Vol. 126, Issue 1
  • DOI: 10.1021/ja0379868

Ti (IV) Complexes with Bidentate O -Chelating N -Heterocyclic Carbenes for Use in the Homopolymerization of Ethylene and Its Copolymerization with Cyclic Olefins
journal, December 2018

  • van der Ende, Melita; Hauser, Philipp M.; Lienert, Christina
  • ChemCatChem, Vol. 11, Issue 2
  • DOI: 10.1002/cctc.201801669

Mono- and Bisionic Mo- and W-Based Schrock Catalysts for Biphasic Olefin Metathesis Reactions in Ionic Liquids
journal, August 2018

  • Schowner, Roman; Elser, Iris; Toth, Florian
  • Chemistry - A European Journal, Vol. 24, Issue 50
  • DOI: 10.1002/chem.201802472

Influence of the Anion of the Salt Used on the Coordination Mode of an N-Heterocyclic Carbene Ligand to Osmium
journal, November 2007

  • Baya, Miguel; Eguillor, Beatriz; Esteruelas, Miguel A.
  • Organometallics, Vol. 26, Issue 26
  • DOI: 10.1021/om700746h

A Mo(VI) Alkylidyne Complex with Polyhedral Oligomeric Silsesquioxane Ligands:  Homogeneous Analogue of a Silica-Supported Alkyne Metathesis Catalyst
journal, November 2006

  • Cho, Hyeon Mo; Weissman, Haim; Wilson, Scott R.
  • Journal of the American Chemical Society, Vol. 128, Issue 46
  • DOI: 10.1021/ja065101x

Beyond Conventional N -Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization
journal, August 2009

  • Schuster, Oliver; Yang, Liangru; Raubenheimer, Helgard G.
  • Chemical Reviews, Vol. 109, Issue 8
  • DOI: 10.1021/cr8005087

Unusual reactivity in organoaluminium and NHC chemistry: deprotonation of AlMe3 by an NHC moiety involving the formation of a sterically bulky NHC–AlMe3 Lewis adduct
journal, January 2010

  • Schmitt, Anne-Laure; Schnee, Gilles; Welter, Richard
  • Chemical Communications, Vol. 46, Issue 14
  • DOI: 10.1039/b922425d

Efficient Room-Temperature Alkyne Metathesis with Well-Defined Imidazolin-2-iminato Tungsten Alkylidyne Complexes
journal, November 2007

  • Beer, Stephan; Hrib, Cristian G.; Jones, Peter G.
  • Angewandte Chemie International Edition, Vol. 46, Issue 46
  • DOI: 10.1002/anie.200703184

Ring-Opening Metathesis Polymerization of Cyclooctyne Employing Well-Defined Tungsten Alkylidyne Complexes
journal, July 2010

  • Lysenko, Sergej; Haberlag, Birte; Wu, Xian
  • Macromolecular Symposia, Vol. 293, Issue 1
  • DOI: 10.1002/masy.200900046

Introducing A Podand Motif to Alkyne Metathesis Catalyst Design: A Highly Active Multidentate Molybdenum(VI) Catalyst that Resists Alkyne Polymerization
journal, March 2011

  • Jyothish, Kuthanapillil; Zhang, Wei
  • Angewandte Chemie International Edition, Vol. 50, Issue 15
  • DOI: 10.1002/anie.201007559