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Title: Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes

Abstract

In the thorium and uranium complexes (C 5Me 5) 2AnMe 2, [(C 5Me 5) 2An(H)(μ-H)] 2 (An = Th, U) and [(C 5Me 5) 2U(H)] 2 dehydrogenate dimethylamine borane (Me2NH·BH3) at room temperature. Upon mild heating at 45 °C, turnover frequencies (TOFs) of 400 h –1 are obtained, which is comparable to some of the fastest Me 2NH·BH 3 dehydrogenation catalysts known in the literature. We propose a β-hydride elimination mechanism for dehydrogenation because of the observation of Me 2N=BH 2, Me 2N=BMe 2, and Me 2N=BHMe in the 11B NMR spectra of catalytic and stoichiometric reactions. The similar catalytic metrics between the actinide dimethyl and hydride complexes with Me 2NH·BH 3 indicate that the actinide hydride complexes are the active catalysts in this chemistry.

Authors:
 [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)
OSTI Identifier:
1375874
Report Number(s):
LA-UR-17-20515
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinide catalysis; thorium and uranium metallocene complexes; pentamethylcyclopentadienyl ligand; dimethylamine borane; dehydrogenation; dehydrocoupling

Citation Formats

Erickson, Karla A., and Kiplinger, Jaqueline L. Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b00967.
Erickson, Karla A., & Kiplinger, Jaqueline L. Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes. United States. doi:10.1021/acscatal.7b00967.
Erickson, Karla A., and Kiplinger, Jaqueline L. Fri . "Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes". United States. doi:10.1021/acscatal.7b00967. https://www.osti.gov/servlets/purl/1375874.
@article{osti_1375874,
title = {Catalytic Dehydrogenation of Dimethylamine Borane by Highly Active Thorium and Uranium Metallocene Complexes},
author = {Erickson, Karla A. and Kiplinger, Jaqueline L.},
abstractNote = {In the thorium and uranium complexes (C5Me5)2AnMe2, [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) and [(C5Me5)2U(H)]2 dehydrogenate dimethylamine borane (Me2NH·BH3) at room temperature. Upon mild heating at 45 °C, turnover frequencies (TOFs) of 400 h–1 are obtained, which is comparable to some of the fastest Me2NH·BH3 dehydrogenation catalysts known in the literature. We propose a β-hydride elimination mechanism for dehydrogenation because of the observation of Me2N=BH2, Me2N=BMe2, and Me2N=BHMe in the 11B NMR spectra of catalytic and stoichiometric reactions. The similar catalytic metrics between the actinide dimethyl and hydride complexes with Me2NH·BH3 indicate that the actinide hydride complexes are the active catalysts in this chemistry.},
doi = {10.1021/acscatal.7b00967},
journal = {ACS Catalysis},
number = 7,
volume = 7,
place = {United States},
year = {Fri May 19 00:00:00 EDT 2017},
month = {Fri May 19 00:00:00 EDT 2017}
}

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