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A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes

Journal Article · · Inorganic Chemistry
 [1];  [2];  [2];  [2];  [3];  [2];  [4];  [4];  [2];  [2];  [3];  [2];  [2];  [2]
  1. Florida State Univ., Tallahassee, FL (United States); Univ. of California, Irvine, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry Division
  2. Florida State Univ., Tallahassee, FL (United States)
  3. Univ. of California, Irvine, CA (United States)
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry Division
+ Show Author Affiliations
Here, an approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C8H8, with a solution obtained from the reduction of Cp'3Pu (Cp' = C5H4SiMe3) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C8H8 by a putative Pu(II) complex, (Cp'3PuII)1–, generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C8H8)2PuIII], 1-Pu, and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp'4PuIII], 2-Pu. Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C8H8)2PuIV, 3-Pu. Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C8H8)2– rings. The (Cp'4PuIII)– anion in 2-Pu features three η5-Cp' rings and one η1-Cp' ring, which is a rare example of a formal Pu–C η1-bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available PuIVO2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu. PuIVO2 was converted to PuIIIBr3(DME)2 (DME = CH3OCH2CH2OCH3) and subsequently PuIIIBr3(THF)x, which was used to independently synthesize 1-Pu, 2-Pu, and 3-Pu.
Research Organization:
Florida State University, Tallahassee, FL (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
Grant/Contract Number:
89233218CNA000001; AC52-06NA25396; SC0004739; SC0010677; SC0016568
OSTI ID:
1680020
Alternate ID(s):
OSTI ID: 2370433
Report Number(s):
LA-UR--20-23097
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 18 Vol. 59; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
actinides
lanthanides
organic polymers
plutonium
redox reactions