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

Abstract

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.

Authors:
 [1];  [2];  [2];  [2]; ORCiD logo [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
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1400126
Alternate Identifier(s):
OSTI ID: 1398571
Report Number(s):
LA-UR-16-26750
Journal ID: ISSN 0022-328X; TRN: US1703099
Grant/Contract Number:  
AC52-06NA25396; CHE-1265608; CHE-1565658; AC05-06OR23100
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Organometallic Chemistry
Additional Journal Information:
Journal Volume: 829; Journal Issue: C; Journal ID: ISSN 0022-328X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Uranium; Pentamethylcyclopentadienyl; Metallacyclocumulene; Electronic spectroscopy; X-ray crystallography

Citation Formats

Pagano, Justin K., Erickson, Karla A., Scott, Brian L., Morris, David E., Waterman, Rory, and Kiplinger, Jaqueline L.. Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph). United States: N. p., 2016. Web. https://doi.org/10.1016/j.jorganchem.2016.10.034.
Pagano, Justin K., Erickson, Karla A., Scott, Brian L., Morris, David E., Waterman, Rory, & Kiplinger, Jaqueline L.. Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph). United States. https://doi.org/10.1016/j.jorganchem.2016.10.034
Pagano, Justin K., Erickson, Karla A., Scott, Brian L., Morris, David E., Waterman, Rory, and Kiplinger, Jaqueline L.. Sat . "Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)". United States. https://doi.org/10.1016/j.jorganchem.2016.10.034. https://www.osti.gov/servlets/purl/1400126.
@article{osti_1400126,
title = {Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph)},
author = {Pagano, Justin K. and Erickson, Karla A. and Scott, Brian L. and Morris, David E. and Waterman, Rory and Kiplinger, Jaqueline L.},
abstractNote = {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.},
doi = {10.1016/j.jorganchem.2016.10.034},
journal = {Journal of Organometallic Chemistry},
number = C,
volume = 829,
place = {United States},
year = {2016},
month = {10}
}

Journal Article:

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Cited by: 9 works
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Figures / Tables:

Scheme 1. Scheme 1.: Known examples of actinide complexes featuring all-carbon metallacycle groups.

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Works referenced in this record:

Olefin Metathesis: The Early Days (Nobel Lecture)
journal, June 2006


Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture)
journal, June 2006

  • Grubbs, Robert H.
  • Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3760-3765
  • DOI: 10.1002/anie.200600680

Multiple Metal–Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture)
journal, June 2006

  • Schrock, Richard R.
  • Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3748-3759
  • DOI: 10.1002/anie.200600085

The Marriage of Metallacycle Transfer Chemistry with Suzuki–Miyaura Cross-Coupling To Give Main Group Element-Containing Conjugated Polymers
journal, March 2013

  • He, Gang; Kang, Le; Torres Delgado, William
  • Journal of the American Chemical Society, Vol. 135, Issue 14
  • DOI: 10.1021/ja402242z

Coaxing Solid-State Phosphorescence from Tellurophenes
journal, March 2014

  • He, Gang; Torres Delgado, William; Schatz, Devon J.
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201307373

Phosphorescence within benzotellurophenes and color tunable tellurophenes under ambient conditions
journal, January 2015

  • He, Gang; Wiltshire, Benjamin D.; Choi, Paul
  • Chemical Communications, Vol. 51, Issue 25
  • DOI: 10.1039/C4CC06529H

Conversion of Zirconacyclopentadienes into Metalloles: Fagan–Nugent Reaction and Beyond
journal, April 2015

  • Yan, Xiaoyu; Xi, Chanjuan
  • Accounts of Chemical Research, Vol. 48, Issue 4
  • DOI: 10.1021/ar500429f

Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds
journal, November 1981

  • Fagan, Paul J.; Manriquez, Juan M.; Maatta, Eric A.
  • Journal of the American Chemical Society, Vol. 103, Issue 22
  • DOI: 10.1021/ja00412a021

[(C5Me5)2U][(µ-Ph)2BPh2] as a four electron reductant
journal, January 2005

  • Evans, William J.; Kozimor, Stosh A.; Ziller, Joseph W.
  • Chemical Communications, Issue 37
  • DOI: 10.1039/b508612d

Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides
journal, January 2015

  • Pagano, Justin K.; Dorhout, Jacquelyn M.; Waterman, Rory
  • Chemical Communications, Vol. 51, Issue 98
  • DOI: 10.1039/C5CC06856H

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

  • Evans, William J.; Miller, Kevin A.; Ziller, Joseph W.
  • Organometallics, Vol. 26, Issue 17
  • DOI: 10.1021/om700382a

Multi-Electron Reduction from Alkyl/Hydride Ligand Combinations in U 4+ Complexes
journal, September 2008

  • Evans, William J.; Montalvo, Elizabeth; Kozimor, Stosh A.
  • Journal of the American Chemical Society, Vol. 130, Issue 37
  • DOI: 10.1021/ja805107v

Uranium and Thorium Hydride Complexes as Multielectron Reductants: A Combined Neutron Diffraction and Quantum Chemical Study
journal, February 2012

  • Grant, Daniel J.; Stewart, Timothy J.; Bau, Robert
  • Inorganic Chemistry, Vol. 51, Issue 6
  • DOI: 10.1021/ic202503h

A thorium metallacyclopentadiene complex: a combined experimental and computational study
journal, January 2015

  • Fang, Bo; Hou, Guohua; Zi, Guofu
  • Dalton Transactions, Vol. 44, Issue 17
  • DOI: 10.1039/C5DT00838G

An Actinide Metallacyclopropene Complex: Synthesis, Structure, Reactivity, and Computational Studies
journal, November 2014

  • Fang, Bo; Ren, Wenshan; Hou, Guohua
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja509770t

Experimental and Computational Studies on an Actinide Metallacyclocumulene Complex
journal, November 2015


C–H bond activation induced by thorium metallacyclopropene complexes: a combined experimental and computational study
journal, January 2015

  • Fang, Bo; Zhang, Lei; Hou, Guohua
  • Chemical Science, Vol. 6, Issue 8
  • DOI: 10.1039/C5SC01684C

Uranium(III)-Mediated C–C-Coupling of Terminal Alkynes: Formation of Dinuclear Uranium(IV) Vinyl Complexes
journal, July 2012

  • Kosog, Boris; Kefalidis, Christos E.; Heinemann, Frank W.
  • Journal of the American Chemical Society, Vol. 134, Issue 30
  • DOI: 10.1021/ja3047393

NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010

  • Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
  • Organometallics, Vol. 29, Issue 9
  • DOI: 10.1021/om100106e

Improved synthesis of (aminocarbene)chromium(0) complexes with use of C8K-generated Cr(CO)52-. Multivariant optimization of an organometallic reaction
journal, October 1990

  • Schwindt, Mark A.; Lejon, Tore; Hegedus, Louis S.
  • Organometallics, Vol. 9, Issue 10
  • DOI: 10.1021/om00160a033

Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene
journal, April 2016

  • Zhang, Lei; Hou, Guohua; Zi, Guofu
  • Journal of the American Chemical Society, Vol. 138, Issue 15
  • DOI: 10.1021/jacs.6b01391

Preparation of (η 5 -C 5 Me 5 ) 2 Th(bipy) and Its Reactivity toward Small Molecules
journal, June 2016


Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes
journal, October 2004

  • Morris, David E.; Da Re, Ryan E.; Jantunen, Kimberly C.
  • Organometallics, Vol. 23, Issue 22
  • DOI: 10.1021/om049634v

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

  • Pellny, Paul-Michael; Kirchbauer, Frank G.; Burlakov, Vladimir V.
  • Journal of the American Chemical Society, Vol. 121, Issue 36
  • DOI: 10.1021/ja991046z

Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV)
journal, August 1970

  • Karraker, David G.; Stone, John Austin.; Jones, Erwin Rudolph.
  • Journal of the American Chemical Society, Vol. 92, Issue 16
  • DOI: 10.1021/ja00719a014

Observation of 239Pu Nuclear Magnetic Resonance
journal, May 2012


Synthesis and cyclic voltammetric study of bis(pentamethylcyclopentadienyl)neptunium dichloride
journal, December 1986


Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory
journal, June 2008

  • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
  • Inorganic Chemistry, Vol. 47, Issue 12
  • DOI: 10.1021/ic8004932

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

  • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 131, Issue 34
  • DOI: 10.1021/ja9015759

Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides
journal, September 2013

  • Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja405844j

The First f-Element Ketimido Complex:  Synthesis and Characterization of (C 5 Me 5 ) 2 U(−NCPh 2 ) 2
journal, June 2002

  • Kiplinger, Jaqueline L.; Morris, David E.; Scott, Brian L.
  • Organometallics, Vol. 21, Issue 15
  • DOI: 10.1021/om020381k

Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds
journal, September 2004

  • Jantunen, Kimberly C.; Burns, Carol J.; Castro-Rodriguez, Ingrid
  • Organometallics, Vol. 23, Issue 20
  • DOI: 10.1021/om0343824

Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides
journal, April 2007

  • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
  • Journal of the American Chemical Society, Vol. 129, Issue 16
  • DOI: 10.1021/ja0686458

Systematic Studies of Early Actinide Complexes:  Uranium(IV) Fluoroketimides
journal, September 2007

  • Schelter, Eric J.; Yang, Ping; Scott, Brian L.
  • Inorganic Chemistry, Vol. 46, Issue 18
  • DOI: 10.1021/ic700455b

    Works referencing / citing this record:

    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

    • Ghorai, Sagar; Jemmis, Eluvathingal D.
    • Chemistry - A European Journal, Vol. 23, Issue 41
    • DOI: 10.1002/chem.201702422

    Recent developments in actinide metallacycles
    journal, January 2018


    Actinide 2-metallabiphenylenes that satisfy Hückel’s rule
    journal, February 2020


    Preparation of a uranium metallacyclocumulene and its reactivity towards unsaturated organic molecules
    journal, January 2017

    • Zhang, Lei; Hou, Guohua; Zi, Guofu
    • Dalton Transactions, Vol. 46, Issue 11
    • DOI: 10.1039/c7dt00396j

    An example of unusual pyridine donor Schiff base uranyl (UO 2 2+ ) complexes
    journal, January 2017

    • Hardy, E. E.; Wyss, K. M.; Eddy, M. A.
    • Chemical Communications, Vol. 53, Issue 42
    • DOI: 10.1039/c7cc02747h

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