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Title: Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions

Abstract

Here, a new bulky silazido ligand, –N(SiHMe 2)Dipp (Dipp = C 6H 3-2,6- iPr 2) supports planar, three-coordinate homoleptic rare earth complexes Ln{N(SiHMe 2)Dipp} 3 (Ln = Sc, Y, Lu) that each contain three secondary Ln←HSi interactions and one agostic CH bond. Y{N(SiHMe 2)Dipp} 3 and acetophenone react via hydrosilylation, rather than by insertion into the Y–N bond or enolate formation.

Authors:
 [1];  [2];  [1];  [3];  [1];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Beijing Normal Univ., Beijing (People's Republic of China)
  3. Iowa State Univ., Ames, IA (United States)
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:
1441001
Alternate Identifier(s):
OSTI ID: 1454335
Report Number(s):
IS-J-9677
Journal ID: ISSN 1359-7345; CHCOFS
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 54; 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 Chathurika, Wan, Suchen, Venkatesh, Amrit, Ellern, Arkady, Rossini, Aaron J., and Sadow, Aaron D. Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions. United States: N. p., 2018. Web. doi:10.1039/C8CC03186J.
Boteju, Kasuni Chathurika, Wan, Suchen, Venkatesh, Amrit, Ellern, Arkady, Rossini, Aaron J., & Sadow, Aaron D. Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions. United States. doi:10.1039/C8CC03186J.
Boteju, Kasuni Chathurika, Wan, Suchen, Venkatesh, Amrit, Ellern, Arkady, Rossini, Aaron J., and Sadow, Aaron D. Tue . "Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions". United States. doi:10.1039/C8CC03186J. https://www.osti.gov/servlets/purl/1441001.
@article{osti_1441001,
title = {Rare Earth Arylsilazido Compounds with Inequivalent Secondary Interactions},
author = {Boteju, Kasuni Chathurika and Wan, Suchen and Venkatesh, Amrit and Ellern, Arkady and Rossini, Aaron J. and Sadow, Aaron D.},
abstractNote = {Here, a new bulky silazido ligand, –N(SiHMe2)Dipp (Dipp = C6H3-2,6-iPr2) supports planar, three-coordinate homoleptic rare earth complexes Ln{N(SiHMe2)Dipp}3 (Ln = Sc, Y, Lu) that each contain three secondary Ln←HSi interactions and one agostic CH bond. Y{N(SiHMe2)Dipp}3 and acetophenone react via hydrosilylation, rather than by insertion into the Y–N bond or enolate formation.},
doi = {10.1039/C8CC03186J},
journal = {ChemComm},
number = ,
volume = 54,
place = {United States},
year = {2018},
month = {6}
}

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

Figures / Tables:

Figure 1 Figure 1: SiH region of 1H NMR spectra of 4 acquired in toluene-d8 from 298 to 205 K.

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Works referenced in this record:

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    Works referencing / citing this record:

    CCDC 1838231: Experimental Crystal Structure Determination: YIGNOU : tris(N-[2,6-diisopropylphenyl]-1,1-dimethylsilanaminato)-scandium
    dataset, April 2018


    CCDC 1838233: Experimental Crystal Structure Determination: YIGPAI : tris(N-[2,6-diisopropylphenyl]-1,1-dimethylsilanaminato)-yttrium
    dataset, April 2018


    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

    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

    Facile Synthesis of Lanthanidocenes by the “Borohydride/Alkyl Route” and Their Application in Isoprene Polymerization
    journal, April 2010

    • Visseaux, Marc; Terrier, Michael; Mortreux, André
    • European Journal of Inorganic Chemistry, Vol. 2010, Issue 18
    • DOI: 10.1002/ejic.201000184

    Synthesis of rare earth metal complexes incorporating amido and enolate mixed ligands: Characterization and reactivity
    journal, September 2008


    β-SiH-Containing Tris(silazido) Rare-Earth Complexes as Homogeneous and Grafted Single-Site Catalyst Precursors for Hydroamination
    journal, January 2017


    Preparation and properties of tantalum imido complexes and their reactions with alkynes. Coordination control through multiple metal-ligand bonding
    journal, October 1989

    • Chao, Yuan Wei; Wexler, Pamela A.; Wigley, David E.
    • Inorganic Chemistry, Vol. 28, Issue 20
    • DOI: 10.1021/ic00319a022

    .eta.2-Silanimine complexes of zirconocene: synthesis, structure, and reactivity of Cp2Zr(.eta.2-SiMe2:N-tert-Bu)(PMe3)
    journal, February 1991

    • Procopio, Leo J.; Carroll, Patrick J.; Berry, Donald H.
    • Journal of the American Chemical Society, Vol. 113, Issue 5
    • DOI: 10.1021/ja00005a083

    Agostic .beta.-silicon-hydrogen interactions in silylamido complexes of zirconocene
    journal, January 1994

    • Procopio, Leo J.; Carroll, Patrick J.; Berry, Donald H.
    • Journal of the American Chemical Society, Vol. 116, Issue 1
    • DOI: 10.1021/ja00080a020

    Lewis Base Mediated β-Elimination and Lewis Acid Mediated Insertion Reactions of Disilazido Zirconium Compounds
    journal, September 2013

    • Yan, KaKing; Duchimaza Heredia, Juan J.; Ellern, Arkady
    • Journal of the American Chemical Society, Vol. 135, Issue 40
    • DOI: 10.1021/ja407950e

    C 2 -Symmetric ansa -Lanthanidocene Complexes. Synthesis via Silylamine Elimination and β-SiH Agostic Rigidity
    journal, April 2000

    • Eppinger, Jörg; Spiegler, Michael; Hieringer, Wolfgang
    • Journal of the American Chemical Society, Vol. 122, Issue 13
    • DOI: 10.1021/ja992786a

    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

    Homoleptic Trivalent Tris(alkyl) Rare Earth Compounds
    journal, November 2017

    • Pindwal, Aradhana; Yan, KaKing; Patnaik, Smita
    • Journal of the American Chemical Society, Vol. 139, Issue 46
    • DOI: 10.1021/jacs.7b09521

    Preparation of cyclodisilazanes from dimethylhydroaminosilanes, (CH3)2Si(H)NHR
    journal, January 1986

    • Wiseman, Gary H.; Wheeler, David R.; Seyferth, Dietmar.
    • Organometallics, Vol. 5, Issue 1
    • DOI: 10.1021/om00132a026

    Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands
    journal, November 2014

    • Goodwin, Conrad A. P.; Joslin, Kristian C.; Lockyer, Selena J.
    • Organometallics, Vol. 34, Issue 11
    • DOI: 10.1021/om501123e

    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

    Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †
    journal, January 1998

    • Anwander, Reiner; Runte, Oliver; Eppinger, Jörg
    • Journal of the Chemical Society, Dalton Transactions, Issue 5
    • DOI: 10.1039/a705608g

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