Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.; Gibson, John K.

doi:10.1039/c6dt02414a

Title: Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

Journal Article · Thu Jul 07 00:00:00 EDT 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/c6dt02414a· OSTI ID:1435062

Dau, Phuong D. ^[1]; Shuh, David K. ^[1]; Sturzbecher-Hoehne, Manuel ^[1]; Abergel, Rebecca J. ^[1]; Gibson, John K. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf^II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf^II(CH₃SO₂)₃-, prepared in the gas phase by reductive elimination of CH₃SO₂ from Cf^III(CH₃SO₂)₄-. Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of CfIII and SmIII, and no evidence for reduction of Cm^III. This reflects the comparative 3+/2+ reduction potentials: Cf³⁺ (-1.60 V) ≈ Sm³⁺ (-1.55 V) >> Cm³⁺ (-3.7 V). Association of O₂ to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf^II coordination complexes and similar chemistry of Cf and Sm.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1435062

Journal Information:: Dalton Transactions, Vol. 45, Issue 31; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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References (35)

Gas-Phase Coordination Complexes of Dipositive Plutonyl, PuO ₂ ²⁺ : Chemical Diversity Across the Actinyl Series Rios, Daniel; Rutkowski, Philip X.; Van Stipdonk, Michael J. Inorganic Chemistry, Vol. 50, Issue 11 https://doi.org/10.1021/ic2005375	journal	June 2011
Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II) MacDonald, Matthew R.; Bates, Jefferson E.; Fieser, Megan E. Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja303357w	journal	May 2012
Stabilization of divalent californium in crystalline strontium tetraborate Peterson, J. R.; Xu, W. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 203, Issue 2 https://doi.org/10.1007/BF02041513	journal	March 1996
First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic051667v	journal	January 2006
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Unusual structure, bonding and properties in a californium borate Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi Nature Chemistry, Vol. 6, Issue 5 https://doi.org/10.1038/nchem.1896	journal	March 2014
Divalent Samarium Compounds with Heavier Chalcogenolate (EPh; E = Se, Te) Ligands Freedman, Deborah; Kornienko, Anna; Emge, Thomas J. Inorganic Chemistry, Vol. 39, Issue 10 https://doi.org/10.1021/ic9913278	journal	May 2000
Heteroleptic Lanthanide Complexes with Aryloxide Ligands. Synthesis and Structural Characterization of Divalent and Trivalent Samarium Aryloxide/Halide and Aryloxide/Cyclopentadienide Complexes Hou, Zhaomin; Fujita, Akira; Yoshimura, Takashi Inorganic Chemistry, Vol. 35, Issue 25 https://doi.org/10.1021/ic960683c	journal	January 1996
Complexes of divalent lanthanides (ytterbium(II), europium(II), and samarium(II)) with decaborates White, James P.; Shore, Sheldon G. Inorganic Chemistry, Vol. 31, Issue 13 https://doi.org/10.1021/ic00039a018	journal	June 1992
Gas Phase Studies of the Pesci Decarboxylation Reaction: Synthesis, Structure, and Unimolecular and Bimolecular Reactivity of Organometallic Ions O’Hair, Richard A. J.; Rijs, Nicole J. Accounts of Chemical Research, Vol. 48, Issue 2 https://doi.org/10.1021/ar500377u	journal	January 2015
Pressure and Density Series Equations of State for Steam as Derived from the Haar–Gallagher–Kell Formulation Dobbins, R. A.; Mohammed, K.; Sullivan, D. A. Journal of Physical and Chemical Reference Data, Vol. 17, Issue 1 https://doi.org/10.1063/1.555819	journal	January 1988
Aluminate Samarium(II) and Samarium(III) Aryloxides. Isolation of a Single-Component Ethylene Polymerization Catalyst Korobkov, Ilia; Gambarotta, Sandro Organometallics, Vol. 28, Issue 14 https://doi.org/10.1021/om900172n	journal	July 2009
Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory Rios, Daniel; Michelini, Maria C.; Lucena, Ana F. Inorganic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ic3001625	journal	June 2012
Who Wins: Pesci, Peters, or Deacon? Intrinsic Reactivity Orders for Organocuprate Formation via Ligand Decomposition Sraj, Lenka O’Connor; Khairallah, George N.; da Silva, Gabriel Organometallics, Vol. 31, Issue 5 https://doi.org/10.1021/om2011722	journal	February 2012
Formation and Characterization of the Uranyl–SO ₂ Complex, UO ₂ (CH ₃ SO ₂ )(SO ₂ ) ⁻ Gong, Yu; Gibson, John K. The Journal of Physical Chemistry A, Vol. 117, Issue 4 https://doi.org/10.1021/jp311034x	journal	January 2013
About low oxidation states, hydration and covalence properties of f elements David, F. H. Radiochimica Acta, Vol. 96, Issue 3 https://doi.org/10.1524/ract.2008.1470	journal	January 2008
The stabilization of divalent californium in the solid state: Californium dibromide Peterson, J. R.; Baybarz, R. D. Inorganic and Nuclear Chemistry Letters, Vol. 8, Issue 4 https://doi.org/10.1016/0020-1650(72)80025-4	journal	April 1972
Electrochemical studies of trivalent californium and selected trivalent lanthanides in aqueous solution Musikas, C.; Haire, R. G.; Peterson, J. R. Journal of Inorganic and Nuclear Chemistry, Vol. 43, Issue 11 https://doi.org/10.1016/0022-1902(81)80646-X	journal	January 1981
Divalent Lanthanide Chemistry: Three Synthetic Routes to Samarium(II) and Ytterbium(II) Bis(phosphido) Species Including the Structural Characterization of Yb[PPh2]2(thf)4 and Sm[PPh2]2(N-MeIm)4 Rabe, Gerd W.; Yap, Glenn P. A.; Rheingold, Arnold L. Inorganic Chemistry, Vol. 34, Issue 18 https://doi.org/10.1021/ic00122a003	journal	August 1995
Novel lanthanide(ii) complexes supported by carbon-bridged biphenolate ligands: synthesis, structure and catalytic activity Deng, Mingyu; Yao, Yingming; Shen, Qi Dalton Transactions, Issue 6 https://doi.org/10.1039/b317027f	journal	January 2004
The 3D quadrupole ion trap mass spectrometer as a complete chemical laboratory for fundamental gas-phase studies of metal mediated chemistry O'Hair, Richard A. J. Chemical Communications, Issue 14 https://doi.org/10.1039/b516348j	journal	January 2006
Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite Dau, Phuong D.; Carretas, José M.; Marçalo, Joaquim Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01385	journal	August 2015
Electrospray production and collisional dissociation of lanthanide/methylsulfonyl anion complexes: Sulfur dioxide anion as a ligand Gong, Yu; Michelini, Maria C.; Gibson, John K. International Journal of Mass Spectrometry, Vol. 392 https://doi.org/10.1016/j.ijms.2015.09.003	journal	December 2015
Two-Electron Three-Centered Bond in Side-On (η ² ) Uranyl(V) Superoxo Complexes Bryantsev, Vyacheslav S.; Jong, Wibe A. de; Cossel, Kevin C. The Journal of Physical Chemistry A, Vol. 112, Issue 26 https://doi.org/10.1021/jp804202q	journal	July 2008
Emergence of californium as the second transitional element in the actinide series Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7827	journal	April 2015
Synthesis and Solid State Structures of Sterically Crowded d ⁰ -Metallocenes of Magnesium, Calcium, Strontium, Barium, Samarium, and Ytterbium Weber, Frank; Schultz, Madeleine; Sofield, Chadwick D. Organometallics, Vol. 21, Issue 15 https://doi.org/10.1021/om0108705	journal	July 2002
Expanding Dinitrogen Reduction Chemistry to Trivalent Lanthanides via the LnZ ₃ /Alkali Metal Reduction System: Evaluation of the Generality of Forming Ln ₂ (μ - η ² ^{: η ² ^{-N ₂ ) Complexes via LnZ ₃ /K}} Evans, William J.; Lee, David S.; Rego, Daniel B. Journal of the American Chemical Society, Vol. 126, Issue 44 https://doi.org/10.1021/ja046047s	journal	November 2004
Evaluation of a Silylene Divalent Lanthanide Interaction in the Metallocene Complex (C ₅ Me ₅ ) ₂ Sm[SiN ^t ^{BuCHCHN ^t ^Bu]} Evans, William J.; Perotti, Jeremy M.; Ziller, Joseph W. Organometallics, Vol. 22, Issue 5 https://doi.org/10.1021/om0208422	journal	March 2003
Studies of californium(II) and (III) iodides Wild, J. F.; Hulet, E. K.; Lougheed, R. W. Journal of Inorganic and Nuclear Chemistry, Vol. 40, Issue 5 https://doi.org/10.1016/0022-1902(78)80157-2	journal	January 1978
Metastable charge-transfer state of californium( iii ) compounds Liu, Guokui; Cary, Samantha K.; Albrecht-Schmitt, Thomas E. Physical Chemistry Chemical Physics, Vol. 17, Issue 24 https://doi.org/10.1039/C5CP01855B	journal	January 2015
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr ²⁺ , Gd ²⁺ , Tb ²⁺ , and Lu ²⁺ MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W. Journal of the American Chemical Society, Vol. 135, Issue 26 https://doi.org/10.1021/ja403753j	journal	May 2013
Effects of changing the M ²⁺ cation on the crystal structure and optical properties of divalent samarium-doped MAl ₂ Si ₂ O ₈ (M = Ca, Sr, Ba) Li, Ling; Liu, Xiaoguang RSC Advances, Vol. 5, Issue 25 https://doi.org/10.1039/C4RA15391J	journal	January 2015
Lanthanide(II) complexes bearing mixed linked and unlinked cyclopentadienyl–monodentate-anionic ligands Hou, Zhaomin; Wakatsuki, Yasuo Journal of Organometallic Chemistry, Vol. 647, Issue 1-2 https://doi.org/10.1016/S0022-328X(01)01237-2	journal	March 2002
Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes: ETD of Uranyl/Plutonyl Complexes Rios, Daniel; Rutkowski, Philip X.; Shuh, David K. Journal of Mass Spectrometry, Vol. 46, Issue 12 https://doi.org/10.1002/jms.2011	journal	December 2011
Polarographic evidence for the divalent oxidation state of californium Friedman, H. A.; Stokely, J. R.; Baybarz, R. D. Inorganic and Nuclear Chemistry Letters, Vol. 8, Issue 5 https://doi.org/10.1016/0020-1650(72)80249-6	journal	May 1972

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