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
 

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)

Journal Article · · Journal of Organometallic Chemistry
 [1];  [2];  [2];  [2];  [3];  [2]
  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)
  3. Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
+ Show Author Affiliations
A new uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph), was synthesized by both reaction of (C5Me5)2UCl2 with 1,4-diphenylbutadiyne in the presence of KC8 and by ligand exchange between (C5Me5)2U(η2-Me3SiC2SiMe3) and 1,4-diphenylbutadiyne. Lastly, full characterization of (C5Me5)2U(η4-1,2,3,4-PhC4Ph) is reported, including the solid-state structure. (C5Me5)2U(η4-1,2,3,4-PhC4Ph) displays an unusually detailed UV–visible spectrum, which is rare for uranium(IV) metallocene complexes.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
Grant/Contract Number:
AC05-06OR23100; AC52-06NA25396
OSTI ID:
1400126
Alternate ID(s):
OSTI ID: 1398571
Report Number(s):
LA-UR--16-26750
Journal Information:
Journal of Organometallic Chemistry, Journal Name: Journal of Organometallic Chemistry Journal Issue: C Vol. 829; ISSN 0022-328X
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (38)

Multiple Metal–Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture) journal June 2006
Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture) journal June 2006
Olefin Metathesis: The Early Days (Nobel Lecture) journal June 2006
Coaxing Solid-State Phosphorescence from Tellurophenes journal March 2014
Synthesis and cyclic voltammetric study of bis(pentamethylcyclopentadienyl)neptunium dichloride journal December 1986
Experimental and Computational Studies on an Actinide Metallacyclocumulene Complex journal November 2015
Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5 ) 2 U(μ-H)] 2 journal February 2016
Preparation of (η 5 -C 5 Me 5 ) 2 Th(bipy) and Its Reactivity toward Small Molecules journal June 2016
Conversion of Zirconacyclopentadienes into Metalloles: Fagan–Nugent Reaction and Beyond journal April 2015
Uranium and Thorium Hydride Complexes as Multielectron Reductants: A Combined Neutron Diffraction and Quantum Chemical Study journal February 2012
Systematic Studies of Early Actinide Complexes:  Uranium(IV) Fluoroketimides journal September 2007
Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory journal June 2008
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV) journal August 1970
Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides journal April 2007
Uranium(III)-Mediated C–C-Coupling of Terminal Alkynes: Formation of Dinuclear Uranium(IV) Vinyl Complexes journal July 2012
The Marriage of Metallacycle Transfer Chemistry with Suzuki–Miyaura Cross-Coupling To Give Main Group Element-Containing Conjugated Polymers journal March 2013
Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides journal September 2013
An Actinide Metallacyclopropene Complex: Synthesis, Structure, Reactivity, and Computational Studies journal November 2014
Multi-Electron Reduction from Alkyl/Hydride Ligand Combinations in U 4+ Complexes journal September 2008
Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory journal September 2009
Reactivity of Permethylzirconocene and Permethyltitanocene toward Disubstituted 1,3-Butadiynes:  η 4 - vs η 2 -Complexation or C−C Coupling with the Permethyltitanocene journal September 1999
Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene journal April 2016
Synthesis and properties of a new class of highly reactive trivalent actinide organometallic compounds. Derivatives of bis(pentamethylcyclopentadienyl)uranium(III) journal January 1982
Improved synthesis of (aminocarbene)chromium(0) complexes with use of C8K-generated Cr(CO)52-. Multivariant optimization of an organometallic reaction journal October 1990
The First f-Element Ketimido Complex:  Synthesis and Characterization of (C 5 Me 5 ) 2 U(−NCPh 2 ) 2 journal June 2002
Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds journal September 2004
Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes journal October 2004
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist journal May 2010
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
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
Phosphorescence within benzotellurophenes and color tunable tellurophenes under ambient conditions journal January 2015
Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides journal January 2015
A thorium metallacyclopentadiene complex: a combined experimental and computational study journal January 2015
C–H bond activation induced by thorium metallacyclopropene complexes: a combined experimental and computational study journal January 2015
[(C5Me5)2U][(µ-Ph)2BPh2] as a four electron reductant journal January 2005
Observation of 239Pu Nuclear Magnetic Resonance journal May 2012

Cited By (6)

δ and φ back-donation in AnIV metallacycles journal March 2020
A DFT Study on the Stabilization of the B≡B Triple Bond in a Metallaborocycle: Contrasting Electronic Structures of Boron and Carbon Analogues journal June 2017
Actinide 2-metallabiphenylenes that satisfy Hückel’s rule journal February 2020
An example of unusual pyridine donor Schiff base uranyl (UO 2 2+ ) complexes journal January 2017
Preparation of a uranium metallacyclocumulene and its reactivity towards unsaturated organic molecules journal January 2017
Recent developments in actinide metallacycles journal January 2018

Figures / Tables (5)

Scheme 1.(p. 3)figure Scheme 1.
Figure 1.(p. 6)figure Figure 1.
Figure 2.(p. 6)figure Figure 2.
Table 1.(p. 7)table Table 1.
Figure 3.(p. 8)figure Figure 3.

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electronic spectroscopy
Metallacyclocumulene
Pentamethylcyclopentadienyl
Uranium
X-ray crystallography