skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Unexpected formal insertion of CO2 into the C-Si bonds of a zinc compound

Abstract

Reaction of [κ2-PR2C(SiMe3)Py]2Zn (R = Ph, 2a; iPr, 2b) with CO2 affords the products of formal insertion at the C–Si bond, [κ2-PR2CC(O)O(SiMe3)Py]2Zn (R = Ph, 3a; iPr, 3b). Insertion product 3b was structurally characterized. As a result, the reaction appears to be a stepwise insertion and rearrangement of CO2 based on kinetic data.

Authors:
 [1];  [2];  [2];  [2];  [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Univ. of Vermont, Burlington, VT (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1235362
Report Number(s):
SAND-2015-7532J
Journal ID: ISSN 1359-7345; CHCOFS; 603475
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 51; Journal Issue: 87; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kemp, Richard A., McGrew, Genette I., Khatri, Pathik A., Geiger, William E., and Waterman, Rory. Unexpected formal insertion of CO2 into the C-Si bonds of a zinc compound. United States: N. p., 2015. Web. doi:10.1039/C5CC06910F.
Kemp, Richard A., McGrew, Genette I., Khatri, Pathik A., Geiger, William E., & Waterman, Rory. Unexpected formal insertion of CO2 into the C-Si bonds of a zinc compound. United States. doi:10.1039/C5CC06910F.
Kemp, Richard A., McGrew, Genette I., Khatri, Pathik A., Geiger, William E., and Waterman, Rory. Tue . "Unexpected formal insertion of CO2 into the C-Si bonds of a zinc compound". United States. doi:10.1039/C5CC06910F. https://www.osti.gov/servlets/purl/1235362.
@article{osti_1235362,
title = {Unexpected formal insertion of CO2 into the C-Si bonds of a zinc compound},
author = {Kemp, Richard A. and McGrew, Genette I. and Khatri, Pathik A. and Geiger, William E. and Waterman, Rory},
abstractNote = {Reaction of [κ2-PR2C(SiMe3)Py]2Zn (R = Ph, 2a; iPr, 2b) with CO2 affords the products of formal insertion at the C–Si bond, [κ2-PR2CC(O)O(SiMe3)Py]2Zn (R = Ph, 3a; iPr, 3b). Insertion product 3b was structurally characterized. As a result, the reaction appears to be a stepwise insertion and rearrangement of CO2 based on kinetic data.},
doi = {10.1039/C5CC06910F},
journal = {ChemComm},
number = 87,
volume = 51,
place = {United States},
year = {2015},
month = {9}
}

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

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: General strategy for CO2 activation using mildly Lewis acidic metals.

Save / Share:

Works referenced in this record:

Structurally simple complexes of CO 2
journal, January 2015

  • Murphy, Luke J.; Robertson, Katherine N.; Kemp, Richard A.
  • Chemical Communications, Vol. 51, Issue 19
  • DOI: 10.1039/C4CC08510H

Cationic zinc complexes: a new class of catalyst for living lactide polymerization at ambient temperature
journal, January 2010

  • Wheaton, Craig A.; Hayes, Paul G.
  • Chemical Communications, Vol. 46, Issue 44
  • DOI: 10.1039/c0cc03463k

Frustrated Lewis Pair Chemistry: Development and Perspectives
journal, May 2015

  • Stephan, Douglas W.; Erker, Gerhard
  • Angewandte Chemie International Edition, Vol. 54, Issue 22
  • DOI: 10.1002/anie.201409800

Frustrated Lewis Pairs: From Concept to Catalysis
journal, December 2014

  • Stephan, Douglas W.
  • Accounts of Chemical Research, Vol. 48, Issue 2
  • DOI: 10.1021/ar500375j

Organocatalysts with carbon-centered activity for CO 2 reduction with boranes
journal, January 2015

  • Yang, Yanxin; Xu, Maotong; Song, Datong
  • Chemical Communications, Vol. 51, Issue 56
  • DOI: 10.1039/C5CC04337A

Formation of Phosphino-Substituted Isocyanate by Reaction of CO 2 with Group 2 Complexes Based on the (Me 3 Si)( i -Pr 2 P)NH Ligand
journal, December 2011

  • Dickie, Diane A.; Gislason, Kevin B.; Kemp, Richard A.
  • Inorganic Chemistry, Vol. 51, Issue 2
  • DOI: 10.1021/ic202399z

Bridged Aminotroponiminate Complexes of Zinc
journal, June 2003

  • Gamer, Michael T.; Roesky, Peter W.
  • European Journal of Inorganic Chemistry, Vol. 2003, Issue 11
  • DOI: 10.1002/ejic.200300008

Formation of a Reversible, Intramolecular Main-Group Metal–CO 2 Adduct
journal, November 2011

  • Dickie, Diane A.; Coker, Eric N.; Kemp, Richard A.
  • Inorganic Chemistry, Vol. 50, Issue 22
  • DOI: 10.1021/ic201697g

Cationic organozinc complexes of a bis(phosphinimine) pincer ligand: synthesis, structural and polymerization studies
journal, January 2010

  • Wheaton, Craig A.; Hayes, Paul G.
  • Dalton Transactions, Vol. 39, Issue 16
  • DOI: 10.1039/b922543a

NH/PH Isomerization and a Lewis Pair for Carbon Dioxide Capture
journal, July 2013

  • Barry, Brian M.; Dickie, Diane A.; Murphy, Luke J.
  • Inorganic Chemistry, Vol. 52, Issue 15
  • DOI: 10.1021/ic401498r

Ruthenium(II) complexes with new tridentate ligands containing P, N, O donor atoms: highly efficient catalysts for transfer hydrogenation of ketones by propan-2-ol
journal, January 1995

  • Yang, Hong; Alvarez, Marie; Lugan, No�l
  • Journal of the Chemical Society, Chemical Communications, Issue 17
  • DOI: 10.1039/c39950001721

Synthesis of Phosphole-2,5-dicarboxylic Acids via a [1,5]-Shift of Carbon Dioxide around the Phosphole Nucleus
journal, April 2002

  • Melaimi, Mohand; Ricard, Louis; Mathey, François
  • Organic Letters, Vol. 4, Issue 8
  • DOI: 10.1021/ol0102895

Electron deficient zinc complexes: Enhanced lactide polymerization activity achieved through rational ligand design
journal, May 2012


Reversible formal insertion of CO2 into a remote C–H bond of a ligand in a Ru(ii) complex at room temperature
journal, January 2012

  • Annibale, Vincent T.; Song, Datong
  • Chemical Communications, Vol. 48, Issue 44
  • DOI: 10.1039/c2cc17933d

A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO 2 to Methanol Using Hydroboranes
journal, June 2013

  • Courtemanche, Marc-André; Légaré, Marc-André; Maron, Laurent
  • Journal of the American Chemical Society, Vol. 135, Issue 25
  • DOI: 10.1021/ja404585p

Der Einflu� der anionischen Liganden auf die Struktur von Nickel(II)- und Kobalt(II)-Komplexen des Bisphenylphosphino-methylpyridins-(2)
journal, June 1968

  • Uhlig, E.; Sch�fer, M.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 359, Issue 1-2
  • DOI: 10.1002/zaac.19683590109

Transition-Metal-Free Catalytic Reduction of Carbon Dioxide
journal, February 2014

  • Fontaine, Frédéric-Georges; Courtemanche, Marc-André; Légaré, Marc-André
  • Chemistry - A European Journal, Vol. 20, Issue 11
  • DOI: 10.1002/chem.201304376

Activated Zinc Complexes Supported by a Neutral, Phosphinimine-Containing Ligand: Synthesis and Efficacy for the Polymerization of Lactide
journal, March 2009

  • Wheaton, Craig A.; Ireland, Benjamin J.; Hayes, Paul G.
  • Organometallics, Vol. 28, Issue 5
  • DOI: 10.1021/om801034k

3-(2-Pyridyl)-5-(2-thienyl)pyrazole and Complexes of Its Anion with Lithium, Magnesium, Calcium, and Zinc Ions
journal, October 2012

  • Kloubert, Tobias; Müller, Christoph; Krieck, Sven
  • European Journal of Inorganic Chemistry, Vol. 2012, Issue 36
  • DOI: 10.1002/ejic.201200876

Insertion of Carbon Dioxide into Main-Group Complexes: Formation of the [N(CO 2 ) 3 ] 3− Ligand
journal, December 2008

  • Dickie, Diane A.; Parkes, Marie V.; Kemp, Richard A.
  • Angewandte Chemie International Edition, Vol. 47, Issue 51
  • DOI: 10.1002/anie.200804218

Structures and CO 2 Reactivity of Zinc Complexes of Bis(diisopropyl-) and Bis(diphenylphosphino)amines
journal, November 2014

  • Dickie, Diane A.; Kemp, Richard A.
  • Organometallics, Vol. 33, Issue 22
  • DOI: 10.1021/om500856p

Transient 2 H -Phospholes as Powerful Synthetic Intermediates in Organophosphorus Chemistry
journal, December 2004

  • Mathey, François
  • Accounts of Chemical Research, Vol. 37, Issue 12
  • DOI: 10.1021/ar030118v

Tuning the Reactivity of an Actor Ligand for Tandem CO 2 and C–H Activations: From Spectator Metals to Metal-Free
journal, October 2013

  • Annibale, Vincent T.; Dalessandro, Daniel A.; Song, Datong
  • Journal of the American Chemical Society, Vol. 135, Issue 43
  • DOI: 10.1021/ja4073832

Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs
journal, August 2009

  • Mömming, Cornelia M.; Otten, Edwin; Kehr, Gerald
  • Angewandte Chemie International Edition, Vol. 48, Issue 36
  • DOI: 10.1002/anie.200901636

Ligand effects and nucleophilic addition to (.eta.3-allyl)palladium complexes. A carbon-13 NMR study
journal, March 1987

  • Aakermark, Bjoern.; Krakenberger, Bertil.; Hansson, Sverker.
  • Organometallics, Vol. 6, Issue 3
  • DOI: 10.1021/om00146a031

Synthesis and evaluation of the bonding properties of a potentially tridentate ligand: 1-(diphenylphosphino)-2-ethoxy-1-(2-pyridyl)ethane
journal, January 1994

  • Alvarez, Marie; Lugan, No�l; Mathieu, Ren�
  • Journal of the Chemical Society, Dalton Transactions, Issue 19
  • DOI: 10.1039/dt9940002755

Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
journal, December 2009

  • Stephan, Douglas W.; Erker, Gerhard
  • Angewandte Chemie International Edition, Vol. 49, Issue 1
  • DOI: 10.1002/anie.200903708

Activation of CO2 and CS2 by (Me3Si)(i-Pr2P)NH and its zinc complex
journal, July 2013


Zinc and Cadmium Tropocoronand Complexes:  Effect of Metal Ion Radius on Macrocyclic Ligand Twist and Fold
journal, June 1997

  • Doerrer, Linda H.; Lippard, Stephen J.
  • Inorganic Chemistry, Vol. 36, Issue 12
  • DOI: 10.1021/ic970033o

Electronic response of a (P,N)-based ligand on metal coordination
journal, January 2004

  • Murso, Alexander; Stalke, Dietmar
  • Dalton Trans., Issue 16
  • DOI: 10.1039/B405680A

    Works referencing / citing this record:

    CCDC 1418439: Experimental Crystal Structure Determination: FUXLAN : bis(2-((Diphenylphosphoranylidene)(trimethylsilyl)methyl)pyridine)-zinc
    dataset, August 2015

    • McGrew, Genette; Khatri, Pathik; Geiger, William
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc1jm038

    CCDC 1418440: Experimental Crystal Structure Determination: FUXLER : bis(Trimethylsilyl (diisopropylphosphoranylidene)(pyridin-2-yl)acetate)-zinc
    dataset, August 2015

    • McGrew, Genette; Khatri, Pathik; Geiger, William
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc1jm049

    Insertion of Carbon Dioxide into Main-Group Complexes: Formation of the [N(CO 2 ) 3 ] 3− Ligand
    journal, December 2008

    • Dickie, Diane A.; Parkes, Marie V.; Kemp, Richard A.
    • Angewandte Chemie International Edition, Vol. 47, Issue 51
    • DOI: 10.1002/anie.200804218

    Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs
    journal, August 2009

    • Mömming, Cornelia M.; Otten, Edwin; Kehr, Gerald
    • Angewandte Chemie International Edition, Vol. 48, Issue 36
    • DOI: 10.1002/anie.200901636

    Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
    journal, December 2009

    • Stephan, Douglas W.; Erker, Gerhard
    • Angewandte Chemie International Edition, Vol. 49, Issue 1
    • DOI: 10.1002/anie.200903708

    Frustrated Lewis Pair Chemistry: Development and Perspectives
    journal, May 2015

    • Stephan, Douglas W.; Erker, Gerhard
    • Angewandte Chemie International Edition, Vol. 54, Issue 22
    • DOI: 10.1002/anie.201409800

    RuBisCO-Inspired CO 2 Activation and Transformation by an Iridium(I) Complex
    journal, January 2018

    • Langer, Jens; Hamza, Andrea; Pápai, Imre
    • Angewandte Chemie International Edition, Vol. 57, Issue 9
    • DOI: 10.1002/anie.201712893

    Transition-Metal-Free Catalytic Reduction of Carbon Dioxide
    journal, February 2014

    • Fontaine, Frédéric-Georges; Courtemanche, Marc-André; Légaré, Marc-André
    • Chemistry - A European Journal, Vol. 20, Issue 11
    • DOI: 10.1002/chem.201304376

    Bridged Aminotroponiminate Complexes of Zinc
    journal, June 2003

    • Gamer, Michael T.; Roesky, Peter W.
    • European Journal of Inorganic Chemistry, Vol. 2003, Issue 11
    • DOI: 10.1002/ejic.200300008

    3-(2-Pyridyl)-5-(2-thienyl)pyrazole and Complexes of Its Anion with Lithium, Magnesium, Calcium, and Zinc Ions
    journal, October 2012

    • Kloubert, Tobias; Müller, Christoph; Krieck, Sven
    • European Journal of Inorganic Chemistry, Vol. 2012, Issue 36
    • DOI: 10.1002/ejic.201200876

    Der Einflu� der anionischen Liganden auf die Struktur von Nickel(II)- und Kobalt(II)-Komplexen des Bisphenylphosphino-methylpyridins-(2)
    journal, June 1968

    • Uhlig, E.; Sch�fer, M.
    • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 359, Issue 1-2
    • DOI: 10.1002/zaac.19683590109

    Electron deficient zinc complexes: Enhanced lactide polymerization activity achieved through rational ligand design
    journal, May 2012


    Activation of CO2 and CS2 by (Me3Si)(i-Pr2P)NH and its zinc complex
    journal, July 2013


    Transient 2 H -Phospholes as Powerful Synthetic Intermediates in Organophosphorus Chemistry
    journal, December 2004

    • Mathey, François
    • Accounts of Chemical Research, Vol. 37, Issue 12
    • DOI: 10.1021/ar030118v

    Frustrated Lewis Pairs: From Concept to Catalysis
    journal, December 2014

    • Stephan, Douglas W.
    • Accounts of Chemical Research, Vol. 48, Issue 2
    • DOI: 10.1021/ar500375j

    Formation of a Reversible, Intramolecular Main-Group Metal–CO 2 Adduct
    journal, November 2011

    • Dickie, Diane A.; Coker, Eric N.; Kemp, Richard A.
    • Inorganic Chemistry, Vol. 50, Issue 22
    • DOI: 10.1021/ic201697g

    Formation of Phosphino-Substituted Isocyanate by Reaction of CO 2 with Group 2 Complexes Based on the (Me 3 Si)( i -Pr 2 P)NH Ligand
    journal, December 2011

    • Dickie, Diane A.; Gislason, Kevin B.; Kemp, Richard A.
    • Inorganic Chemistry, Vol. 51, Issue 2
    • DOI: 10.1021/ic202399z

    NH/PH Isomerization and a Lewis Pair for Carbon Dioxide Capture
    journal, July 2013

    • Barry, Brian M.; Dickie, Diane A.; Murphy, Luke J.
    • Inorganic Chemistry, Vol. 52, Issue 15
    • DOI: 10.1021/ic401498r

    Zinc and Cadmium Tropocoronand Complexes:  Effect of Metal Ion Radius on Macrocyclic Ligand Twist and Fold
    journal, June 1997

    • Doerrer, Linda H.; Lippard, Stephen J.
    • Inorganic Chemistry, Vol. 36, Issue 12
    • DOI: 10.1021/ic970033o

    A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO 2 to Methanol Using Hydroboranes
    journal, June 2013

    • Courtemanche, Marc-André; Légaré, Marc-André; Maron, Laurent
    • Journal of the American Chemical Society, Vol. 135, Issue 25
    • DOI: 10.1021/ja404585p

    Tuning the Reactivity of an Actor Ligand for Tandem CO 2 and C–H Activations: From Spectator Metals to Metal-Free
    journal, October 2013

    • Annibale, Vincent T.; Dalessandro, Daniel A.; Song, Datong
    • Journal of the American Chemical Society, Vol. 135, Issue 43
    • DOI: 10.1021/ja4073832

    Synthesis of Phosphole-2,5-dicarboxylic Acids via a [1,5]-Shift of Carbon Dioxide around the Phosphole Nucleus
    journal, April 2002

    • Melaimi, Mohand; Ricard, Louis; Mathey, François
    • Organic Letters, Vol. 4, Issue 8
    • DOI: 10.1021/ol0102895

    Ligand effects and nucleophilic addition to (.eta.3-allyl)palladium complexes. A carbon-13 NMR study
    journal, March 1987

    • Aakermark, Bjoern.; Krakenberger, Bertil.; Hansson, Sverker.
    • Organometallics, Vol. 6, Issue 3
    • DOI: 10.1021/om00146a031

    Structures and CO 2 Reactivity of Zinc Complexes of Bis(diisopropyl-) and Bis(diphenylphosphino)amines
    journal, November 2014

    • Dickie, Diane A.; Kemp, Richard A.
    • Organometallics, Vol. 33, Issue 22
    • DOI: 10.1021/om500856p

    Activated Zinc Complexes Supported by a Neutral, Phosphinimine-Containing Ligand: Synthesis and Efficacy for the Polymerization of Lactide
    journal, March 2009

    • Wheaton, Craig A.; Ireland, Benjamin J.; Hayes, Paul G.
    • Organometallics, Vol. 28, Issue 5
    • DOI: 10.1021/om801034k

    Electronic response of a (P,N)-based ligand on metal coordination
    journal, January 2004

    • Murso, Alexander; Stalke, Dietmar
    • Dalton Trans., Issue 16
    • DOI: 10.1039/b405680a

    Cationic organozinc complexes of a bis(phosphinimine) pincer ligand: synthesis, structural and polymerization studies
    journal, January 2010

    • Wheaton, Craig A.; Hayes, Paul G.
    • Dalton Transactions, Vol. 39, Issue 16
    • DOI: 10.1039/b922543a

    Cationic zinc complexes: a new class of catalyst for living lactide polymerization at ambient temperature
    journal, January 2010

    • Wheaton, Craig A.; Hayes, Paul G.
    • Chemical Communications, Vol. 46, Issue 44
    • DOI: 10.1039/c0cc03463k

    Reversible formal insertion of CO2 into a remote C–H bond of a ligand in a Ru(ii) complex at room temperature
    journal, January 2012

    • Annibale, Vincent T.; Song, Datong
    • Chemical Communications, Vol. 48, Issue 44
    • DOI: 10.1039/c2cc17933d

    Ruthenium(II) complexes with new tridentate ligands containing P, N, O donor atoms: highly efficient catalysts for transfer hydrogenation of ketones by propan-2-ol
    journal, January 1995

    • Yang, Hong; Alvarez, Marie; Lugan, No�l
    • Journal of the Chemical Society, Chemical Communications, Issue 17
    • DOI: 10.1039/c39950001721

    Structurally simple complexes of CO 2
    journal, January 2015

    • Murphy, Luke J.; Robertson, Katherine N.; Kemp, Richard A.
    • Chemical Communications, Vol. 51, Issue 19
    • DOI: 10.1039/c4cc08510h

    Organocatalysts with carbon-centered activity for CO 2 reduction with boranes
    journal, January 2015

    • Yang, Yanxin; Xu, Maotong; Song, Datong
    • Chemical Communications, Vol. 51, Issue 56
    • DOI: 10.1039/c5cc04337a

    Insertion of CO 2 into the carbon–boron bond of a boronic ester ligand
    journal, January 2016

    • Janes, Trevor; Osten, Kimberly M.; Pantaleo, Adam
    • Chemical Communications, Vol. 52, Issue 22
    • DOI: 10.1039/c6cc01257d

    Zwitterionic indenylammonium with carbon-centred reactivity towards reversible CO 2 binding and catalytic reduction
    journal, January 2017

    • Yang, Yanxin; Yan, Linfan; Xie, Qinyu
    • Organic & Biomolecular Chemistry, Vol. 15, Issue 10
    • DOI: 10.1039/c7ob00364a

    Synthesis and evaluation of the bonding properties of a potentially tridentate ligand: 1-(diphenylphosphino)-2-ethoxy-1-(2-pyridyl)ethane
    journal, January 1994

    • Alvarez, Marie; Lugan, No�l; Mathieu, Ren�
    • Journal of the Chemical Society, Dalton Transactions, Issue 19
    • DOI: 10.1039/dt9940002755

    RuBisCO-Inspired CO 2 Activation and Transformation by an Iridium(I) Complex
    journal, January 2018

    • Langer, Jens; Hamza, Andrea; Pápai, Imre
    • Angewandte Chemie International Edition, Vol. 57, Issue 9
    • DOI: 10.1002/anie.201712893

    Insertion of CO 2 into the carbon–boron bond of a boronic ester ligand
    journal, January 2016

    • Janes, Trevor; Osten, Kimberly M.; Pantaleo, Adam
    • Chemical Communications, Vol. 52, Issue 22
    • DOI: 10.1039/c6cc01257d

    Zwitterionic indenylammonium with carbon-centred reactivity towards reversible CO 2 binding and catalytic reduction
    journal, January 2017

    • Yang, Yanxin; Yan, Linfan; Xie, Qinyu
    • Organic & Biomolecular Chemistry, Vol. 15, Issue 10
    • DOI: 10.1039/c7ob00364a

    RuBisCO-inspirierte CO 2 -Aktivierung und Umwandlung durch einen Iridium(I)-Komplex
    journal, January 2018


    2-Arylsilacyclobutane as a Latent Carbanion Reacting with CO 2
    journal, August 2018

    • Ishida, Naoki; Okumura, Shintaro; Kawasaki, Tairin
    • Angewandte Chemie International Edition, Vol. 57, Issue 35
    • DOI: 10.1002/anie.201805333

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.