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Title: Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS 2P(R 2C 12H 6) (R = H or tBu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS 2P(R 2C 12H 6) in reasonable yields (~60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S 2P(R 2C 12H 6) 1- anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPh 4 1+; Z = P or As). Coordination chemistry between [S 2P( tBu 2C 12H 6)] 1- and [S 2P(C 6H 5)2] 1- with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of UIV and NpIV were redox stable relative to those of UIII, whereas reactions involving PuIV gave intractable material. For instance, reactions involving UIV and NpIV generated An[S 2P( tBu 2C 12H 6)] 4 and An[S 2P(C 6H 5) 2] 4 whereas reactions between PuIV and [S 2P(C 6H 5) 2] 1- generated a mixture of products from which we postulated a transientmore » PuIII species based on UV-Vis spectroscopy. However, the trivalent Pu[S 2P(C 6H 5) 2] 3(NC 5H 5) 2 compound is stable and could be isolated from reactions between [S 2P(C 6H 5) 2] 1- and the trivalent PuI 3(NC 5H 5) 4 starting material. Attempts to synthesize analogous trivalent compounds with UIII provided the tetravalent U[S 2P(C 6H 5 )2] 4 oxidation product.« less
Authors:
 [1] ;  [2] ;  [2] ;  [3] ;  [2] ;  [4] ;  [2] ;  [2] ;  [2] ;  [2] ;  [2] ;  [2]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Illinois, Champaign-Urbana, IL (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Iowa, Iowa City, IA (United States)
  4. Univ. of Illinois, Champaign-Urbana, IL (United States)
Publication Date:
Report Number(s):
LA-UR-15-24054
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 43; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1331261

Macor, Joseph A., Brown, Jessie L., Cross, Justin Neil, Daly, Scott R., Gaunt, Andrew James, Girolami, Gregory S., Janicke, Michael Timothy, Kozimor, Stosh Anthony, Neu, Mary P., Olson, Angela Christine, Reilly, Sean Douglas, and Scott, Brian Lindley. Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu. United States: N. p., Web. doi:10.1039/C5DT02976G.
Macor, Joseph A., Brown, Jessie L., Cross, Justin Neil, Daly, Scott R., Gaunt, Andrew James, Girolami, Gregory S., Janicke, Michael Timothy, Kozimor, Stosh Anthony, Neu, Mary P., Olson, Angela Christine, Reilly, Sean Douglas, & Scott, Brian Lindley. Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu. United States. doi:10.1039/C5DT02976G.
Macor, Joseph A., Brown, Jessie L., Cross, Justin Neil, Daly, Scott R., Gaunt, Andrew James, Girolami, Gregory S., Janicke, Michael Timothy, Kozimor, Stosh Anthony, Neu, Mary P., Olson, Angela Christine, Reilly, Sean Douglas, and Scott, Brian Lindley. 2015. "Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu". United States. doi:10.1039/C5DT02976G. https://www.osti.gov/servlets/purl/1331261.
@article{osti_1331261,
title = {Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu},
author = {Macor, Joseph A. and Brown, Jessie L. and Cross, Justin Neil and Daly, Scott R. and Gaunt, Andrew James and Girolami, Gregory S. and Janicke, Michael Timothy and Kozimor, Stosh Anthony and Neu, Mary P. and Olson, Angela Christine and Reilly, Sean Douglas and Scott, Brian Lindley},
abstractNote = {New members of the dithiophosphinic acid family of potential actinide extractants were prepared: heterocyclic 2,2'-biphenylenedithiophosphinic acids of stoichiometry HS2P(R2C12H6) (R = H or tBu). The time- and atom-efficient syntheses afforded multigram quantities of pure HS2P(R2C12H6) in reasonable yields (~60%). These compounds differed from other diaryldithiophosphinic acid extractants in that the two aryl groups were connected to one another at the ortho positions to form a 5-membered dibenzophosphole ring. These 2,2'-biphenylenedithiophosphinic acids were readily deprotonated to form S2P(R2C12H6)1- anions, which were crystallized as salts with tetraphenylpnictonium cations (ZPh41+; Z = P or As). Coordination chemistry between [S2P(tBu2C12H6)]1- and [S2P(C6H5)2]1- with U, Np, and Pu was comparatively investigated. The results showed that dithiophosphinate complexes of UIV and NpIV were redox stable relative to those of UIII, whereas reactions involving PuIV gave intractable material. For instance, reactions involving UIV and NpIV generated An[S2P(tBu2C12H6)]4 and An[S2P(C6H5)2]4 whereas reactions between PuIV and [S2P(C6H5)2]1- generated a mixture of products from which we postulated a transient PuIII species based on UV-Vis spectroscopy. However, the trivalent Pu[S2P(C6H5)2]3(NC5H5)2 compound is stable and could be isolated from reactions between [S2P(C6H5)2]1- and the trivalent PuI3(NC5H5)4 starting material. Attempts to synthesize analogous trivalent compounds with UIII provided the tetravalent U[S2P(C6H5)2]4 oxidation product.},
doi = {10.1039/C5DT02976G},
journal = {Dalton Transactions},
number = 43,
volume = 44,
place = {United States},
year = {2015},
month = {1}
}

Works referenced in this record:

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