Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b06090· OSTI ID:1843644
 [1];  [2];  [3];  [3];  [4];  [3];  [3];  [5];  [3];  [3]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States); Program Manager, Catalysis Science Office of Basic Energy Sciences U.S. Department of Energy
  2. Korea Advanced Inst. of Science and Technology (KAIST), Daejeon (Korea, Republic of); Inst. for Basic Science (IBS), Daejeon (Korea, Republic of)
  3. Univ. of Pennsylvania, Philadelphia, PA (United States)
  4. Inst. for Basic Science (IBS), Daejeon (Korea, Republic of)
  5. Inst. for Basic Science (IBS), Daejeon (Korea, Republic of); Korea Advanced Inst. of Science and Technology (KAIST), Daejeon (Korea, Republic of)
+ Show Author Affiliations
Uranium complexes in the +3 and +4 oxidation states were prepared using the anionic PN– (PN– = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) ligand framework. New complexes include the halide starting materials, (PN)2UIIII (1) and (PN)2UIVCl2 (2), which both yield (PN)2UIV(N3)2 (3) by reaction with NaN3. Compound 3 was reduced with potassium graphite to produce a putative, transient uranium–nitrido moiety that underwent an intramolecular C–H activation to form a rare example of a parent imido complex, [K(THF)3][(PN)UIV(=NH)[iPr2P(C6H3Me)N(C6H2Me2CH2)]] (4). Here, calculated reaction energy profiles strongly suggest that a C–H insertion becomes unfavorable when a reductant is present, offering a distinctively different reaction pathway than previously observed for other uranium nitride complexes.
Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
SC0012486
OSTI ID:
1843644
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 36 Vol. 140; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

References (46)

Activation of Carbon–Hydrogen Bonds via 1,2-RH-Addition/-Elimination to Early Transition Metal Imides journal February 2018
Challenging the Metallocene Dominance in Actinide Chemistry with a Soft PNP Pincer Ligand: New Uranium Structures and Reactivity Patterns journal May 2009
Synthesis of Terminal Vanadium(V) Imido, Oxo, Sulfido, Selenido, and Tellurido Complexes by Imido Group or Chalcogenide Atom Transfer to Trigonal Monopyramidal V[N3N] (N3N = [(Me3SiNCH2CH2)3N]3-) journal March 1994
A four coordinate parent imidevia a titanium nitridyl journal January 2012
Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine journal September 2014
Uranium azide photolysis results in C–H bond activation and provides evidence for a terminal uranium nitride journal July 2010
A Nitrido Salt Reagent of Titanium journal May 2014
A Highly Reactive Uranium Complex Supported by the Calix[4]tetrapyrrole Tetraanion Affording Dinitrogen Cleavage, Solvent Deoxygenation, and Polysilanol Depolymerization journal September 2002
Synthesis, Structure, and Characterization of the Hydrogen-Substituted Imido Complex TiCl 2 (NH)(OPPh 3 ) 2 journal January 1996
Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia journal April 2014
A Nitrido-Centered Uranium Azido Cluster Obtained from a Uranium Azide journal April 2008
Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride journal April 2014
Rhenium complex of a triply deprotonated chelated thiosemicarbazide and its conversion to a nitride complex via a hydrazide intermediate. Crystal structure of [ReCl2(NH)(NHNH2)(PPh3)2] journal January 1995
Synthesis and Structure of a Terminal Uranium Nitride Complex journal June 2012
Structural elucidation of a mononuclear titanium methylidene journal January 2017
A Simple Preparative Route to Bis(imido)uranium(VI) Complexes by the Direct Reductions of Diazenes and Azides journal April 1998
N–N Bond Cleavage of Mid-Valent Ta(IV) Hydrazido and Hydrazidium Complexes Relevant to the Schrock Cycle for Dinitrogen Fixation journal June 2013
N−N Bond Cleavage of Organohydrazines by Molybdenum(II) and Tungsten(II) Complexes Containing a Linear Tetraphosphine Ligand. Formation of Nitrido or Imido Complexes and Their Reactivities journal August 2007
Molybdenum(IV) complexes with terminal imido- and nitrido-ligands the crystal and molecular structures of [MoN(N3)(Ph2P(CH2)2PPh2)2] and [MoBr(NH)(Ph2P(CH2)2PPh2)2] Br·MeOH journal January 1983
Synthesis of Heteroleptic Uranium (μ−η 6 :η 6 -C 6 H 6 ) 2− Sandwich Complexes via Facile Displacement of (η 5 -C 5 Me 5 ) 1− by Ligands of Lower Hapticity and Their Conversion to Heteroleptic Bis(imido) Compounds journal December 2009
A Molecularly Defined, Grafted Olefin Metathesis Catalyst from Tris(neopentyl)-nitridomolybdenum(VI) journal December 1996
Mononuclear and Terminally Bound Titanium Nitrides journal July 2015
Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U( v ) oxo and nitrido complexes journal January 2016
Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr( iii ) and Hf( iii ) journal January 2018
Reactivity differences between molecular and surface silanols in the preparation of homogeneous and heterogeneous olefin metathesis catalysts journal November 2005
Molecular titanium nitrides: nucleophiles unleashed journal January 2017
Studies Relevant to Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum Triamidoamine Complexes journal February 2005
Synthesis and structure of the first uranium(VI) organometallic complex journal December 1992
Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N3)(PMe3)3 with azide as the oxidant journal April 2011
Recent advances in the chemistry of nitrogen fixation journal December 1978
The preparation, crystal and molecular structure of [MoCl2(NH)O(EtPh2PO)2] the preparation, crystal and molecular structure of [MoCl2(NH)O(EtPh2PO)2]. An example of terminal, nonlinear-imido-coordination journal January 1979
Isolation and characterization of a uranium(VI)–nitride triple bond journal May 2013
Nitrogen reduction and functionalization by a multimetallic uranium nitride complex journal July 2017
What a Difference a 5f Element Makes: Trivalent and Tetravalent Uranium Halide Complexes Supported by One and Two Bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) Ligands journal March 2009
Nitridotris(neopentyl)molybdenum(VI) journal June 1994
Reactions of Nitridorhenium(V) and -Osmium(VI) Complexes with Acylating Agents journal May 1999
Isolation and Characterization of the Osmium(V)–Imido Complex [OsV(Tp)(Cl)2(NH)] We are grateful to the National Science Foundation under Grant number CHE-9503738, the Los Alamos National Laboratory (DOE) under Grant Number 10730-001-00-2C, and the Laboratory Directed Research and Development Program for support of this research. M. H. V. Huynh gratefully acknowledges postdoctoral fellowship support from the Directorapos;s Office of Los Alamos National Laboratory. Los Alamos National Laboratory is operated by the University of California for the U.S. Department of Energy under Contract W-7405-ENG-36. We also thank Dr. Paul R. Sharp (Professor of Chemistry, University of Missouri, Columbia, MO, 65211) for the information on transition metal parent imido complexes. journal November 2001
Vanadium Complexes of the N(CH 2 CH 2 S) 3 3- and O(CH 2 CH 2 S) 2 2- Ligands with Coligands Relevant to Nitrogen Fixation Processes journal July 2000
Investigation of Uranium Tris(imido) Complexes: Synthesis, Characterization, and Reduction Chemistry of [U(NDIPP) 3 (thf) 3 ] journal July 2015
Osmium Phosphiniminato Complexes:  Synthesis, Protonation, Structure, and Redox-Coupled Hydrolytic Scission of N−P Bonds journal June 2003
Energetics and Mechanism of Ammonia Synthesis through the Chatt Cycle: Conditions for a Catalytic Mode and Comparison with the Schrock Cycle journal January 2008
An Experimental and Computational Analysis of the Formation of the Terminal Nitrido Complex (η 3 -Cp*) 2 Mo(N)(N 3 ) by Elimination of N 2 from Cp* 2 Mo(N 3 ) 2 :  The Barrier to Elimination Is Strongly Influenced by the exo versus endo Configuration of the Azide Ligand journal September 2001
Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions journal April 2017
Harnessing redox activity for the formation of uranium tris(imido) compounds journal July 2014
Synthese und Struktur von [Re(NH)Cl2(PMe2Ph)3][TaCl6] und [(Me2PhP)3Cl2Re≡N]2VOCl2 journal November 1998
Hydride Transfer Reactivity of Mo(L)(H)(depe)2 (L = N, NBEt3) journal February 2006

Similar Records

Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(iii) and Hf(iii)
Journal Article · Thu Jan 25 23:00:00 EST 2018 · ChemComm · OSTI ID:1843641
Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes
Journal Article · Tue Apr 04 20:00:00 EDT 2017 · Inorganic Chemistry · OSTI ID:1348217

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Extrusion
Ligands
Nitrides
Oxidation state
Uranium