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Title: Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C 5Me 4SiMe 3) 2(H)(thf)

Abstract

The use of the bulky cyclopentadienyl ligand Cp' (Cp' = C 5Me 4SiMe 3) to stabilize cerium hydrides has resulted here in the preparation of two novel tuck-in complexes with C–H activated SiMe 3 groups. Subsequent reaction of these with H 2 in thf gives a lanthanide terminal hydride species Ce(Cp') 2(H)(thf) which reversibly regenerates the tuck-in complex under sustained vacuum. This compound is only the second structurally characterized terminal cerium hydride. This new hydride is a catalyst in H/D exchange reactions between with both sp 3-CH and sp 2-CH bonds, and for the hydrogenation of unsaturated alkene bonds.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); LANL Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1489942
Report Number(s):
LA-UR-15-20988
Journal ID: ISSN 1434-1948
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2016; Journal Issue: 28; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrides; C–H activation; lanthanides; cerium

Citation Formats

Summerscales, Owen T., Batista, Enrique R., Scott, Brian L., Wilkerson, Marianne P., and Sutton, Andrew D. Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C5Me4SiMe3)2(H)(thf). United States: N. p., 2016. Web. doi:10.1002/ejic.201600737.
Summerscales, Owen T., Batista, Enrique R., Scott, Brian L., Wilkerson, Marianne P., & Sutton, Andrew D. Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C5Me4SiMe3)2(H)(thf). United States. doi:10.1002/ejic.201600737.
Summerscales, Owen T., Batista, Enrique R., Scott, Brian L., Wilkerson, Marianne P., and Sutton, Andrew D. Thu . "Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C5Me4SiMe3)2(H)(thf)". United States. doi:10.1002/ejic.201600737. https://www.osti.gov/servlets/purl/1489942.
@article{osti_1489942,
title = {Reversible Formation of a Cerium-Bound Terminal Hydride: Ce(C5Me4SiMe3)2(H)(thf)},
author = {Summerscales, Owen T. and Batista, Enrique R. and Scott, Brian L. and Wilkerson, Marianne P. and Sutton, Andrew D.},
abstractNote = {The use of the bulky cyclopentadienyl ligand Cp' (Cp' = C5Me4SiMe3) to stabilize cerium hydrides has resulted here in the preparation of two novel tuck-in complexes with C–H activated SiMe3 groups. Subsequent reaction of these with H2 in thf gives a lanthanide terminal hydride species Ce(Cp')2(H)(thf) which reversibly regenerates the tuck-in complex under sustained vacuum. This compound is only the second structurally characterized terminal cerium hydride. This new hydride is a catalyst in H/D exchange reactions between with both sp3-CH and sp2-CH bonds, and for the hydrogenation of unsaturated alkene bonds.},
doi = {10.1002/ejic.201600737},
journal = {European Journal of Inorganic Chemistry},
number = 28,
volume = 2016,
place = {United States},
year = {2016},
month = {8}
}

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Free Publicly Available Full Text
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Cited by: 7 works
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Figures / Tables:

Scheme 1 Scheme 1: Synthetic routes to previously known cerium and lanthanide hydride complexes.

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Works referenced in this record:

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Reactions of Monomeric [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH and CO with or without H 2 :  An Experimental and Computational Study
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    Works referencing / citing this record:

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    Hydride complexes of the transition metals
    journal, June 1972


    Two [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH Molecules are Involved in Hydrogenation of Pyridine to Piperidine as Shown by Experiments and Computations
    journal, April 2014

    • Perrin, Lionel; Werkema, Evan L.; Eisenstein, Odile
    • Inorganic Chemistry, Vol. 53, Issue 13
    • DOI: 10.1021/ic500133y

    Organolanthanide hydride chemistry. 1. Synthesis and x-ray crystallographic characterization of dimeric organolanthanide and organoyttrium hydride complexes
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    • Evans, William J.; Meadows, James H.; Wayda, Andrea L.
    • Journal of the American Chemical Society, Vol. 104, Issue 7
    • DOI: 10.1021/ja00371a035

    Hydrogen for Fluorine Exchange in C 6 F 6 and C 6 F 5 H by Monomeric [1,3,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH:  Experimental and Computational Studies
    journal, January 2005

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    • Journal of the American Chemical Society, Vol. 127, Issue 1
    • DOI: 10.1021/ja0451012

    Hydrogen for Fluorine Exchange in CH 4 - x F x by Monomeric [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH:  Experimental and Computational Studies
    journal, June 2005

    • Werkema, Evan L.; Messines, Elsa; Perrin, Lionel
    • Journal of the American Chemical Society, Vol. 127, Issue 21
    • DOI: 10.1021/ja0504800

    Reactions of Monomeric [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH and CO with or without H 2 :  An Experimental and Computational Study
    journal, March 2007

    • Werkema, Evan L.; Maron, Laurent; Eisenstein, Odile
    • Journal of the American Chemical Society, Vol. 129, Issue 9
    • DOI: 10.1021/ja066482h

    Bis(pentamethylcyclopentadienyl) complexes of cerium(III). Crystal structure of (C5Me5)2CeCH(SiMe3)2
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    • Heeres, Hero J.; Renkema, Jaap.; Booij, Martin.
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    Lanthanide Terminal Hydride Complexes Bearing Two Sterically Demanding C 5 Me 4 SiMe 3 Ligands. Synthesis, Structure, and Reactivity
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.