Title: Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides

Journal Article · · ChemComm
DOI: https://doi.org/10.1039/C5CC06856H · OSTI ID:1402588
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  3. Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
  4. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
+ Show Author Affiliations

The thorium and uranium dihydride dimer complexes [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) have been easily prepared using phenylsilane, which is an efficient and safer alternative to hydrogen gas. We demonstrated the synthetic utility of this new hydriding method by the preparation of a variety of organometallic complexes, including, for the first time, (C5Me5)2U(SMe)2, (C5Me5)2Th(C4Ph4), (C5Me5)2U(C4Ph4), (C5Me5)2ThS5, and (C5Me5)2U(bipy) using [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) as multi-electron reductants.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-06OR23100; AC52-06NA25396
OSTI ID:
1402588
Report Number(s):
LA-UR--15-26274
Journal Information:
ChemComm, Journal Name: ChemComm Journal Issue: 98 Vol. 51; ISSN CHCOFS; ISSN 1359-7345
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (35)

Lanthanide(III)/Actinide(III) Differentiation in the Cerium and Uranium Complexes [M(C5Me5)2(L)]0,+ (L=2,2′-Bipyridine, 2,2′:6′,2′′-Terpyridine): Structural, Magnetic, and Reactivity Studies journal November 2005
Synthesis of a hydride-rich uranium-rhenium dimer: [(p-F-C6H4)3P]2ReH6U(η-C5H5)3 journal September 1986
Derivatives of U(BH4)4 and its Lewis base adducts; synthesis of monocyclopentadienyl- and hydride-uranium(IV) complexes: (η-C5H5)U(BH4)3 and (CH3OCH2CH2OCH3)U(BH4)3H journal July 1988
Anionic triscyclopentadienyluranium(III) hydrides journal November 1992
A re-examination of the neptunium-hydrogen system journal March 1987
The upper limit of flammability of hydrogen in air, oxygen, and oxygen-inert mixtures at elevated pressures journal December 1971
The insertion of carbon dioxide into actinide alkyl and hydride bonds journal September 1985
Dehydrocoupling reactions of amines with silanes catalyzed by [(Et2N)3U][BPh4] journal September 2000
Et2SiH2 assisted the selective dimerization of terminal alkynes catalyzed by Cp*2UMe2 journal March 2003
Crystal structure of the uranium oxo borohydride complex U2(μ-O)(BH4)6(dme)2 (dme=1,2-dimethoxyethane) and reformulation of U2(μ-H)2(BH4)6(dme)2 journal February 2012
Organometallic Complexes of Bulky, Optically Active, C 3 -Symmetric Tris(4 S -isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (To P *) journal July 2015
Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements journal October 1997
Uranium and Thorium Hydride Complexes as Multielectron Reductants: A Combined Neutron Diffraction and Quantum Chemical Study journal February 2012
Crystal and molecular structure of hydridotris[bis(trimethylsilyl)amido]uranium(IV) journal February 1981
Organoactinide-catalyzed oligomerization of terminal acetylenes journal June 1995
Preparation and characterization of the first organoactinide polysulfide (.eta.5-C5Me5)2ThS5. A unique example of the twist-boat conformation of the MS5 ring journal January 1986
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
Hydrido[tris(hexamethyldisilylamido)]thorium(IV) and -uranium(IV) journal May 1979
Catalytic Coupling of Terminal Alkynes with Isonitriles Promoted by Organoactinide Complexes journal September 2004
Multi-Electron Reduction from Alkyl/Hydride Ligand Combinations in U 4+ Complexes journal September 2008
Synthesis and properties of a new class of highly reactive trivalent actinide organometallic compounds. Derivatives of bis(pentamethylcyclopentadienyl)uranium(III) journal January 1982
Carbon monoxide activation by organoactinides. Formyl pathways in CO homologation and hydrogenation journal December 1982
Actinide Metallocene Hydride Chemistry: C–H Activation in Tetramethylcyclopentadienyl Ligands to Form [μ-η 5 -C 5 Me 3 H(CH 2 )- κC ] 2– Tuck-over Ligands in a Tetrathorium Octahydride Complex journal October 2013
Solvent-Free Organometallic Reactivity: Synthesis of Hydride and Carboxylate Complexes of Uranium and Yttrium from Gas/Solid Reactions journal December 2013
Actinide Hydride Complexes as Multielectron Reductants:  Analogous Reduction Chemistry from [(C 5 Me 5 ) 2 UH] 2 , [(C 5 Me 5 ) 2 UH 2 ] 2 , and [(C 5 Me 5 ) 2 ThH 2 ] 2 journal July 2007
Formation of (C 5 Me 5 ) 2 U(EPh)Me, (C 5 Me 5 ) 2 U(EPh) 2 , and (C 5 Me 5 ) 2 U( η 2 -TeC 6 H 4 ) from (C 5 Me 5 ) 2 UMe 2 and PhEEPh (E = S, Se, Te) journal August 2007
Coupling of Terminal Alkynes and Isonitriles by Organoactinide Complexes: Scope and Mechanistic Insights journal July 2008
Catalytic Hydrosilylation of Terminal Alkynes Promoted by Organoactinides journal November 1999
Reductive heterocoupling mediated by Cp* 2 U(2,2′-bpy) journal January 2012
Reactions of cp 3 UCl (cp =η-C 5 H 5 ) with various reducing agents: synthesis and crystal structure of the uranium( III ) hydride [(cp 3 U) 2 (µ-H)][Na(THF) 2 ](THF = tetrahydrofuran) journal January 1989
(η 5 -C 5 H 4 SiMe 3 ) 3 UH: the first stable organouranium( IV ) hydride journal January 1991
A thorium metallacyclopentadiene complex: a combined experimental and computational study journal January 2015
Synthesis and some reactions of tris(cyclopentadienyl)-uranium( IV ) hydrides; crystal structure of [U(C 5 H 4 Bu t ) 3 H] journal January 1992
[(C5Me5)2U][(µ-Ph)2BPh2] as a four electron reductant journal January 2005
Bent thorocene complexes with the cyanide, azide and hydride ligands journal January 2013

Cited By (7)

Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium-Carbene or Thorium-Ylide Complexes journal September 2017
Actinide 2-metallabiphenylenes that satisfy Hückel’s rule journal February 2020
Intrinsic reactivity of a uranium metallacyclopropene toward unsaturated organic molecules journal January 2016
Preparation of a uranium metallacyclocumulene and its reactivity towards unsaturated organic molecules journal January 2017
Recent developments in actinide metallacycles journal January 2018
Current advances in the catalytic conversion of carbon dioxide by molecular catalysts: an update journal January 2018
Monomeric thorium dihydrido complexes: versatile precursors to actinide metallacycles journal January 2019

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY