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Title: Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

Abstract

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1435062
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 31; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dau, Phuong D., Shuh, David K., Sturzbecher-Hoehne, Manuel, Abergel, Rebecca J., and Gibson, John K.. Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II). United States: N. p., 2016. Web. doi:10.1039/c6dt02414a.
Dau, Phuong D., Shuh, David K., Sturzbecher-Hoehne, Manuel, Abergel, Rebecca J., & Gibson, John K.. Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II). United States. doi:10.1039/c6dt02414a.
Dau, Phuong D., Shuh, David K., Sturzbecher-Hoehne, Manuel, Abergel, Rebecca J., and Gibson, John K.. Thu . "Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)". United States. doi:10.1039/c6dt02414a. https://www.osti.gov/servlets/purl/1435062.
@article{osti_1435062,
title = {Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)},
author = {Dau, Phuong D. and Shuh, David K. and Sturzbecher-Hoehne, Manuel and Abergel, Rebecca J. and Gibson, John K.},
abstractNote = {The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which CfII is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, CfII(CH3SO2)3-, prepared in the gas phase by reductive elimination of CH3SO2 from CfIII(CH3SO2)4-. Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of CfIII and SmIII, and no evidence for reduction of CmIII. This reflects the comparative 3+/2+ reduction potentials: Cf3+ (-1.60 V) ≈ Sm3+ (-1.55 V) >> Cm3+ (-3.7 V). Association of O2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for CfII coordination complexes and similar chemistry of Cf and Sm.},
doi = {10.1039/c6dt02414a},
journal = {Dalton Transactions},
number = 31,
volume = 45,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2016},
month = {Thu Jul 07 00:00:00 EDT 2016}
}

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Works referenced in this record:

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976