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

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/C5DT02976G· OSTI ID:1331261
 [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)
+ Show Author Affiliations

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.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1331261
Report Number(s):
LA-UR-15-24054; ICHBD9
Journal Information:
Dalton Transactions, Vol. 44, Issue 43; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

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Cited By (11)

Comparing the 2,2′-Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium journal September 2016
Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization journal June 2020
A Straightforward Synthesis of 1,2-Azaphosphindoles: A Straightforward Synthesis of 1,2-Azaphosphindoles journal May 2017
N-Heterocyclic Carbene Adducts of Phenyldioxophosphorane and Its Heavier Sulfur and Selenium Analogues: N-Heterocyclic Carbene Adducts of Phenyldioxophosphorane and Its Heavier Sulfur and Selenium Analogues journal August 2017
Synthesis and characterization of potassium aryl- and alkyl-substituted silylchalcogenolate ligands journal January 2016
Recent studies of the synthesis, functionalization, optoelectronic properties and applications of dibenzophospholes journal January 2017
f-Block complexes of a m -terphenyl dithiocarboxylate ligand journal January 2018
Remarkable structural effects on the complexation of actinides with H-phosphonates: a combined experimental and quantum chemical study journal January 2018
New main-group ferrocenyldithiocarbamates and conversion to ferrocene oxazolidine-2-thione and -2-one journal January 2020
Comparing the 2,2′-Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium journal September 2016
Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization text January 2020

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