Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

Joseph A Macor; Jessie L Brown; Justin N Cross; Scott R Daly; Andrew J Gaunt; Gregory S Girolami; Michael T Janicke; Stosh A Kozimor; Mary P Neu; Angela C Olson; Sean D Reilly; Brian L Scott

doi:10.1039/C5DT02976G

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Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

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Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu

Joseph A Macor, Jessie L Brown, Justin N Cross, Scott R Daly, Andrew J Gaunt, Gregory S Girolami, Michael T Janicke, Stosh A Kozimor, Mary P Neu, Angela C Olson, …

Dalton transactions : an international journal of inorganic chemistry, Vol.44(43), pp.18923-18936

2015

DOI: 10.1039/C5DT02976G

PMID: 26466973

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Abstract

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.

Details

Title: Subtitle: Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu
Creators: Joseph A Macor - Los Alamos National Laboratory, Los Alamos, USA, University of Illinois at Urbana-Champaign, Urbana
Jessie L Brown - Los Alamos National Laboratory, Los Alamos, USA
Justin N Cross - Los Alamos National Laboratory, Los Alamos, USA
Scott R Daly - Los Alamos National Laboratory, Los Alamos, USA, The University of Iowa, Iowa City
Andrew J Gaunt - Los Alamos National Laboratory, Los Alamos, USA
Gregory S Girolami - University of Illinois at Urbana-Champaign, Urbana, USA
Michael T Janicke - Los Alamos National Laboratory, Los Alamos, USA
Stosh A Kozimor - Los Alamos National Laboratory, Los Alamos, USA
Mary P Neu - Los Alamos National Laboratory, Los Alamos, USA
Angela C Olson - Los Alamos National Laboratory, Los Alamos, USA
Sean D Reilly - Los Alamos National Laboratory, Los Alamos, USA
Brian L Scott - Los Alamos National Laboratory, Los Alamos, USA
Resource Type: Journal article
Publication Details: Dalton transactions : an international journal of inorganic chemistry, Vol.44(43), pp.18923-18936
DOI: 10.1039/C5DT02976G
PMID: 26466973
NLM abbreviation: Dalton Trans
ISSN: 1477-9226
eISSN: 1477-9234
Language: English
Date published: 2015
Academic Unit: Chemistry
Record Identifier: 9983985815402771

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