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

Title: Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand

Abstract

Here, a β-SiH functionalized benzyl anion [C(SiHMe2)2Ph]$-$s obtained by deprotonation of HC(SiHMe2)2Ph with KCH2Ph or by reaction of KOtBu and (Me2HSi)3CPh; LnI3(THF)n and three equivalents of this carbanion combine to provide homoleptic tris(alkyl)lanthanide compounds Ln{C(SiHMe2)2Ph}3 (Ln = La, Ce, Pr, Nd) containing secondary metal–ligand interactions.

Authors:
 [1];  [1];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1342922
Report Number(s):
IS-J-9147
Journal ID: ISSN 1359-7345; CHCOFS
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 53; Journal Issue: 4; 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

Boteju, Kasuni C., Ellern, Arkady, and Sadow, Aaron D. Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand. United States: N. p., 2016. Web. doi:10.1039/C6CC09304C.
Boteju, Kasuni C., Ellern, Arkady, & Sadow, Aaron D. Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand. United States. doi:10.1039/C6CC09304C.
Boteju, Kasuni C., Ellern, Arkady, and Sadow, Aaron D. Mon . "Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand". United States. doi:10.1039/C6CC09304C. https://www.osti.gov/servlets/purl/1342922.
@article{osti_1342922,
title = {Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand},
author = {Boteju, Kasuni C. and Ellern, Arkady and Sadow, Aaron D.},
abstractNote = {Here, a β-SiH functionalized benzyl anion [C(SiHMe2)2Ph]$-$s obtained by deprotonation of HC(SiHMe2)2Ph with KCH2Ph or by reaction of KOtBu and (Me2HSi)3CPh; LnI3(THF)n and three equivalents of this carbanion combine to provide homoleptic tris(alkyl)lanthanide compounds Ln{C(SiHMe2)2Ph}3 (Ln = La, Ce, Pr, Nd) containing secondary metal–ligand interactions.},
doi = {10.1039/C6CC09304C},
journal = {ChemComm},
number = 4,
volume = 53,
place = {United States},
year = {2016},
month = {12}
}

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

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Tris(trimethylsilyl)silyllithium · 3 THF: a stable crystalline silyllithium reagent
journal, February 1982


Synthesis and Catalytic Properties of Phenylene-Bridged Binuclear Organolanthanide Complexes
journal, January 2008

  • Yuen, Holming F.; Marks, Tobin J.
  • Organometallics, Vol. 27, Issue 2
  • DOI: 10.1021/om7008952

Lanthanide N , N -Dimethylaminodiboranates: Highly Volatile Precursors for the Deposition of Lanthanide-Containing Thin Films
journal, February 2010

  • Daly, Scott R.; Kim, Do Young; Yang, Yu
  • Journal of the American Chemical Society, Vol. 132, Issue 7
  • DOI: 10.1021/ja9098005

Ziegler-Natta polymerization: the lanthanide model
journal, January 1982

  • Watson, Patricia L.
  • Journal of the American Chemical Society, Vol. 104, Issue 1
  • DOI: 10.1021/ja00365a083

Synthesis and structural characterisation of the first neutral homoleptic lanthanide metal(III) alkyls: [LnR3][Ln = La or Sm, R = CH(SiMe3)2]
journal, January 1988

  • Hitchcock, Peter B.; Lappert, Michael F.; Smith, Richard G.
  • Journal of the Chemical Society, Chemical Communications, Issue 15
  • DOI: 10.1039/c39880001007

Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe 2 ) 3 ) 2 THF 2 (M = Ca, Yb)
journal, October 2009

  • Yan, KaKing; Upton, Brianna M.; Ellern, Arkady
  • Journal of the American Chemical Society, Vol. 131, Issue 42
  • DOI: 10.1021/ja9070865

Trimethylyttrium and Trimethyllutetium
journal, August 2005

  • Dietrich, H. Martin; Raudaschl-Sieber, Gabriele; Anwander, Reiner
  • Angewandte Chemie International Edition, Vol. 44, Issue 33
  • DOI: 10.1002/anie.200463109

α , α -Bis(trimethylsilyl)-Substituted Benzyl Complexes of Potassium and Calcium
journal, November 2000

  • Feil, Florian; Harder, Sjoerd
  • Organometallics, Vol. 19, Issue 24
  • DOI: 10.1021/om0006209

Homoleptic Lanthanide Alkyl and Amide Precatalysts Efficiently Mediate Intramolecular Hydrophosphination/Cyclization. Observations on Scope and Mechanism
journal, November 2003

  • Kawaoka, Amber M.; Douglass, Michael R.; Marks, Tobin J.
  • Organometallics, Vol. 22, Issue 23
  • DOI: 10.1021/om030439a

A tris(alkyl)yttrium compound containing six β-agostic Si–H interactions
journal, January 2009

  • Yan, KaKing; Pawlikowski, Andrew V.; Ebert, Chris
  • Chem. Commun., Issue 6
  • DOI: 10.1039/B818630H

Lanthanum Tribenzyl Complexes as Convenient Starting Materials for Organolanthanum Chemistry
journal, July 2006

  • Bambirra, Sergio; Meetsma, Auke; Hessen, Bart
  • Organometallics, Vol. 25, Issue 14
  • DOI: 10.1021/om060262v

Homoleptic Divalent Dialkyl Lanthanide-Catalyzed Cross-Dehydrocoupling of Silanes and Amines
journal, May 2016


A New and Easy Route to Polysilanylpotassium Compounds
journal, February 1998


Synthesis and crystal structures of organometallic compounds containing the ligands C(SiMe3)2(SiMe2H) and C(SiMe2Ph)2(SiMe2H)
journal, April 2004


Synthesis and Reactivity of Homoleptic α-Metalated N,N -Dimethylbenzylamine Rare-Earth-Metal Complexes
journal, August 2011

  • Behrle, Andrew C.; Schmidt, Joseph A. R.
  • Organometallics, Vol. 30, Issue 15
  • DOI: 10.1021/om200363z

Organometallic compounds of the lanthanides. Part 17. Tris[(tetramethylethylenediamine)lithium] hexamethyl derivatives of the rare earths
journal, January 1984

  • Schumann, Herbert; Mueller, Jochen; Bruncks, Norbert
  • Organometallics, Vol. 3, Issue 1
  • DOI: 10.1021/om00079a013

Some derivatives of tris(dimethylsilyl)methane. A novel bicyclic tris(disiloxane) with a manxane structure
journal, August 1983


Facile C–H activation by lutetium–methyl and lutetium–hydride complexes
journal, January 1983


Lanthanide tri-benzyl complexes: structural variations and useful precursors to phosphorus-stabilised lanthanide carbenes
journal, January 2010

  • Wooles, Ashley J.; Mills, David P.; Lewis, William
  • Dalton Trans., Vol. 39, Issue 2
  • DOI: 10.1039/B911717B

Intermolecular β-Hydrogen Abstraction in Ytterbium, Calcium, and Potassium Tris(dimethylsilyl)methyl Compounds
journal, January 2013

  • Yan, KaKing; Schoendorff, George; Upton, Brianna M.
  • Organometallics, Vol. 32, Issue 5
  • DOI: 10.1021/om3010299

Implementation of Ln(AlMe 4 ) 3 as Precursors in Postlanthanidocene Chemistry
journal, July 2006

  • Zimmermann, Melanie; Törnroos, Karl W.; Anwander, Reiner
  • Organometallics, Vol. 25, Issue 15
  • DOI: 10.1021/om060244d

Structural Characterization of a Tris-Agostic LanthanoidHSi Interaction
journal, March 1996

  • Rees, William S.; Just, Oliver; Schumann, Herbert
  • Angewandte Chemie International Edition in English, Vol. 35, Issue 4
  • DOI: 10.1002/anie.199604191

Homoleptic Rare-Earth Metal Complexes Containing Ln−C σ-Bonds
journal, October 2010

  • Zimmermann, Melanie; Anwander, Reiner
  • Chemical Reviews, Vol. 110, Issue 10
  • DOI: 10.1021/cr1001194

The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy
journal, March 2016

  • Conley, Matthew P.; Lapadula, Giuseppe; Sanders, Kevin
  • Journal of the American Chemical Society, Vol. 138, Issue 11
  • DOI: 10.1021/jacs.6b00071

Komplexkatalyse
journal, March 2001


Phenylene-Bridged Binuclear Organolanthanide Complexes as Catalysts for Intramolecular and Intermolecular Hydroamination
journal, April 2009

  • Yuen, Holming F.; Marks, Tobin J.
  • Organometallics, Vol. 28, Issue 8
  • DOI: 10.1021/om9000023

β-Si−H Agostic Rigidity in a Solvent-Free Indenyl-Derived ansa -Yttrocene Silylamide
journal, April 1997

  • Herrmann, Wolfgang A.; Eppinger, Jörg; Spiegler, Michael
  • Organometallics, Vol. 16, Issue 9
  • DOI: 10.1021/om9608925

Cerium-Catalyzed Hydrosilylation of Acrylates to Give α-Silyl Esters
journal, November 2016

  • Pindwal, Aradhana; Patnaik, Smita; Everett, William C.
  • Angewandte Chemie International Edition, Vol. 56, Issue 2
  • DOI: 10.1002/anie.201610263

    Works referencing / citing this record:

    CCDC 1517683: Experimental Crystal Structure Determination: UCATUQ : tris(η2-bis(dimethylsilyl)(phenyl)methanide)-lanthanum pentane solvate
    dataset, November 2016


    CCDC 1517686: Experimental Crystal Structure Determination: UCATOK : tris(η2-bis(dimethylsilyl)(phenyl)methanide)-praseodymium
    dataset, November 2016


    Structural Characterization of a Tris-Agostic LanthanoidHSi Interaction
    journal, March 1996

    • Rees, William S.; Just, Oliver; Schumann, Herbert
    • Angewandte Chemie International Edition in English, Vol. 35, Issue 4
    • DOI: 10.1002/anie.199604191

    Trimethylyttrium and Trimethyllutetium
    journal, August 2005

    • Dietrich, H. Martin; Raudaschl-Sieber, Gabriele; Anwander, Reiner
    • Angewandte Chemie International Edition, Vol. 44, Issue 33
    • DOI: 10.1002/anie.200463109

    Cerium-Catalyzed Hydrosilylation of Acrylates to Give α-Silyl Esters
    journal, November 2016

    • Pindwal, Aradhana; Patnaik, Smita; Everett, William C.
    • Angewandte Chemie International Edition, Vol. 56, Issue 2
    • DOI: 10.1002/anie.201610263

    Synthesis and crystal structures of organometallic compounds containing the ligands C(SiMe3)2(SiMe2H) and C(SiMe2Ph)2(SiMe2H)
    journal, April 2004


    Homoleptic Divalent Dialkyl Lanthanide-Catalyzed Cross-Dehydrocoupling of Silanes and Amines
    journal, May 2016


    Homoleptic Rare-Earth Metal Complexes Containing Ln−C σ-Bonds
    journal, October 2010

    • Zimmermann, Melanie; Anwander, Reiner
    • Chemical Reviews, Vol. 110, Issue 10
    • DOI: 10.1021/cr1001194

    Ziegler-Natta polymerization: the lanthanide model
    journal, January 1982

    • Watson, Patricia L.
    • Journal of the American Chemical Society, Vol. 104, Issue 1
    • DOI: 10.1021/ja00365a083

    Lewis Acid-Mediated β-Hydride Abstraction Reactions of Divalent M(C(SiHMe 2 ) 3 ) 2 THF 2 (M = Ca, Yb)
    journal, October 2009

    • Yan, KaKing; Upton, Brianna M.; Ellern, Arkady
    • Journal of the American Chemical Society, Vol. 131, Issue 42
    • DOI: 10.1021/ja9070865

    Lanthanide N , N -Dimethylaminodiboranates: Highly Volatile Precursors for the Deposition of Lanthanide-Containing Thin Films
    journal, February 2010

    • Daly, Scott R.; Kim, Do Young; Yang, Yu
    • Journal of the American Chemical Society, Vol. 132, Issue 7
    • DOI: 10.1021/ja9098005

    The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy
    journal, March 2016

    • Conley, Matthew P.; Lapadula, Giuseppe; Sanders, Kevin
    • Journal of the American Chemical Society, Vol. 138, Issue 11
    • DOI: 10.1021/jacs.6b00071

    α , α -Bis(trimethylsilyl)-Substituted Benzyl Complexes of Potassium and Calcium
    journal, November 2000

    • Feil, Florian; Harder, Sjoerd
    • Organometallics, Vol. 19, Issue 24
    • DOI: 10.1021/om0006209

    Organometallic compounds of the lanthanides. Part 17. Tris[(tetramethylethylenediamine)lithium] hexamethyl derivatives of the rare earths
    journal, January 1984

    • Schumann, Herbert; Mueller, Jochen; Bruncks, Norbert
    • Organometallics, Vol. 3, Issue 1
    • DOI: 10.1021/om00079a013

    Homoleptic Lanthanide Alkyl and Amide Precatalysts Efficiently Mediate Intramolecular Hydrophosphination/Cyclization. Observations on Scope and Mechanism
    journal, November 2003

    • Kawaoka, Amber M.; Douglass, Michael R.; Marks, Tobin J.
    • Organometallics, Vol. 22, Issue 23
    • DOI: 10.1021/om030439a

    Implementation of Ln(AlMe 4 ) 3 as Precursors in Postlanthanidocene Chemistry
    journal, July 2006

    • Zimmermann, Melanie; Törnroos, Karl W.; Anwander, Reiner
    • Organometallics, Vol. 25, Issue 15
    • DOI: 10.1021/om060244d

    Lanthanum Tribenzyl Complexes as Convenient Starting Materials for Organolanthanum Chemistry
    journal, July 2006

    • Bambirra, Sergio; Meetsma, Auke; Hessen, Bart
    • Organometallics, Vol. 25, Issue 14
    • DOI: 10.1021/om060262v

    Synthesis and Reactivity of Homoleptic α-Metalated N,N -Dimethylbenzylamine Rare-Earth-Metal Complexes
    journal, August 2011

    • Behrle, Andrew C.; Schmidt, Joseph A. R.
    • Organometallics, Vol. 30, Issue 15
    • DOI: 10.1021/om200363z

    Intermolecular β-Hydrogen Abstraction in Ytterbium, Calcium, and Potassium Tris(dimethylsilyl)methyl Compounds
    journal, January 2013

    • Yan, KaKing; Schoendorff, George; Upton, Brianna M.
    • Organometallics, Vol. 32, Issue 5
    • DOI: 10.1021/om3010299

    Synthesis and Catalytic Properties of Phenylene-Bridged Binuclear Organolanthanide Complexes
    journal, January 2008

    • Yuen, Holming F.; Marks, Tobin J.
    • Organometallics, Vol. 27, Issue 2
    • DOI: 10.1021/om7008952

    Phenylene-Bridged Binuclear Organolanthanide Complexes as Catalysts for Intramolecular and Intermolecular Hydroamination
    journal, April 2009

    • Yuen, Holming F.; Marks, Tobin J.
    • Organometallics, Vol. 28, Issue 8
    • DOI: 10.1021/om9000023

    β-Si−H Agostic Rigidity in a Solvent-Free Indenyl-Derived ansa -Yttrocene Silylamide
    journal, April 1997

    • Herrmann, Wolfgang A.; Eppinger, Jörg; Spiegler, Michael
    • Organometallics, Vol. 16, Issue 9
    • DOI: 10.1021/om9608925

    Synthesis and structural characterisation of the first neutral homoleptic lanthanide metal(III) alkyls: [LnR3][Ln = La or Sm, R = CH(SiMe3)2]
    journal, January 1988

    • Hitchcock, Peter B.; Lappert, Michael F.; Smith, Richard G.
    • Journal of the Chemical Society, Chemical Communications, Issue 15
    • DOI: 10.1039/c39880001007

    Rare earth arylsilazido compounds with inequivalent secondary interactions
    journal, January 2018

    • Boteju, Kasuni C.; Wan, Suchen; Venkatesh, Amrit
    • Chemical Communications, Vol. 54, Issue 53
    • DOI: 10.1039/c8cc03186j

    Rare earth arylsilazido compounds with inequivalent secondary interactions
    journal, January 2018

    • Boteju, Kasuni C.; Wan, Suchen; Venkatesh, Amrit
    • Chemical Communications, Vol. 54, Issue 53
    • DOI: 10.1039/c8cc03186j