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Title: Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

Journal Article · · Inorganica Chimica Acta
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Two new uranium metallacyclopropenes, (C5Me4R)2U(η2-Ph2PC=CPPh2) (R = Me, Et) were prepared by reducing the corresponding (C5Me4R)2UCl2 complexes with KC8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph2P–C≡C–PPh2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C5Me5)2U(η2-Me3SiC=CSiMe3) are discussed. Finally, also presented is the solid-state structure of (C5Me4Et)2U(η2-Ph2PC=CPPh2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylene (Ph2P–C≡C–PPh2) ligand.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1454999
Alternate ID(s):
OSTI ID: 1601299
Report Number(s):
LA-UR-17-31363; TRN: US1901188
Journal Information:
Inorganica Chimica Acta, Vol. 482; ISSN 0020-1693
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

References (25)

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph) journal February 2017
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Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene journal April 2016
Preparation of (η 5 -C 5 Me 5 ) 2 Th(bipy) and Its Reactivity toward Small Molecules journal June 2016
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
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
A thorium metallacyclopentadiene complex: a combined experimental and computational study journal January 2015
Steric and Electronic Influences of Internal Alkynes on the Formation of Thorium Metallacycles: A Combined Experimental and Computational Study journal January 2016
Uranium(III)-Mediated C–C-Coupling of Terminal Alkynes: Formation of Dinuclear Uranium(IV) Vinyl Complexes journal July 2012
An Actinide Metallacyclopropene Complex: Synthesis, Structure, Reactivity, and Computational Studies journal November 2014
C–H bond activation induced by thorium metallacyclopropene complexes: a combined experimental and computational study journal January 2015
Novel acetylene complexes of titanocene and permethyltitanocene without additional ligands. Synthesis spectral characteristics and X-ray diffraction study journal August 1994
Synthesis, Characterization and Reactivity of Group 4 Metallocene Bis(diphenylphosphino)acetylene Complexes—A Reactivity and Bonding Study journal November 2013
Breaking the rules journal June 2013
Metallacyclocumulenes: A Theoretical Perspective on the Structure, Bonding, and Reactivity journal August 2014
Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes journal December 2016
Synthesis, characterization and catalytic activity of the complex titanium bis(dimethylmalonate)–bis(diethylamido) in the polymerization of propylene journal February 2007
A Nitrido Salt Reagent of Titanium journal May 2014
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist journal May 2010
1,4-Dicyanobenzene as a Scaffold for the Preparation of Bimetallic Actinide Complexes Exhibiting Metal-Metal Communication journal September 2008
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Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes journal October 2004
Facile Access to Pentavalent Uranium Organometallics:  One-Electron Oxidation of Uranium(IV) Imido Complexes with Copper(I) Salts journal October 2007
Tetravalent and Pentavalent Uranium Acetylide Complexes Prepared by Oxidative Functionalization with CuCCPh journal July 2008
Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding journal April 2008

Linked Research (2)

Figures / Tables (6)

Figure 1(p. 4)figure Figure 1
Figure 2(p. 6)figure Figure 2
Figure 3(p. 6)figure Figure 3
Figure 4(p. 7)figure Figure 4
Figure 5(p. 7)figure Figure 5
Table 1(p. 8)table Table 1

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Uranium
Phosphorous
Metallacyclopropene
Electronic Spectroscopy
X-ray Crystallography