TY - JOUR
T1 - A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes
AU - Windorff, Cory J.
AU - Sperling, Joseph M.
AU - Albrecht-Schönzart, Thomas E.
AU - Bai, Zhuanling
AU - Evans, William J.
AU - Gaiser, Alyssa N.
AU - Gaunt, Andrew J.
AU - Goodwin, Conrad A.P.
AU - Hobart, David E.
AU - Huffman, Zachary K.
AU - Huh, Daniel N.
AU - Klamm, Bonnie E.
AU - Poe, Todd N.
N1 - Funding Information:
The authors wish to thank Dr. Stosh A. Kozimor for valuable discussions and advice, as well as storage of reagents during initial experiments. Spectroscopic efforts were supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences, through the Center for Actinide Science and Technology (CAST) (T.E.A.S., contract DE-SC0016568), synthetic efforts were supported by the Department of Energy, Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, Heavy Element Chemistry program (T.E.A.S., contract DE-FG02-13ER16414; W.J.E., contract DE-SC0004739; A.J.G., contract DE-AC52-06NA25396), the Office of Workforce Development for Teachers and Scientists, the Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program, administered by the Oak Ridge Institute for Science and Education (ORISE) managed by ORAU (contract DE-AC05-06OR23100, C.J.W.), and the Los Alamos National Laboratory LDRD office named Fellowship program (Distinguished J. Robert Oppenheimer Postdoctoral Fellowship, C.A.P.G.).
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/9/21
Y1 - 2020/9/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85091324569&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.0c01671
DO - 10.1021/acs.inorgchem.0c01671
M3 - Article
C2 - 32910649
AN - SCOPUS:85091324569
SN - 0020-1669
VL - 59
SP - 13301
EP - 13314
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -