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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. doi: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. doi: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. doi: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}
}

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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 referencing / citing this record:

CCDC 1501132: Experimental Crystal Structure Determination: AYUBAZ : (1,4-diphenylbuta-1,2,3-triene)-bis(pentamethyl-cyclopentadienyl)-uranium
dataset, August 2016


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

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

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

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