Californium gleaming

Albrecht‐Schmitt, Thomas E.

doi:10.1038/nchem.2035

Cited by 3 publications

(13 citation statements)

References 5 publications

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“…The second system is one that has proven to be exquisitely sensitive to the nature of the actinide ions employed in the reaction. In this case, we have shown that polyborates form unique structural topologies with each of the different actinide ions from Pu(III) to Cf(III) (7)(8)(9)25).…”

Section: Discussionmentioning

confidence: 85%

“…9.15(3)17.50(2) 23.45(7) ..................................................................................................................................................................................................................... 25 9.07(7) 17.23(2) 23.14(1) ..................................................................................................................................................................................................................... 45 8.8(1) 16.85(6) 22.43(4) ..................................................................................................................................................................................................................... DH (kJ mol −1 ) -19(1) -36(1) -64(3) ..................................................................................................................................................................................................................... DS (J mol −1 K −1 ) 108(5) 209(3) 230(10) ..................................................................................................................................................................................................................... RESEARCH | RESEARCH ARTICLE on October 7, 2020 http://science.sciencemag.org/ Downloaded from…”

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confidence: 99%

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Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state

Silver

Cary

Johnson

et al. 2016

Science

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Berkelium is positioned at a crucial location in the actinide series between the inherently stable half-filled 5f(7) configuration of curium and the abrupt transition in chemical behavior created by the onset of a metastable divalent state that starts at californium. However, the mere 320-day half-life of berkelium's only available isotope, (249)Bk, has hindered in-depth studies of the element's coordination chemistry. Herein, we report the synthesis and detailed solid-state and solution-phase characterization of a berkelium coordination complex, Bk(III)tris(dipicolinate), as well as a chemically distinct Bk(III) borate material for comparison. We demonstrate that berkelium's complexation is analogous to that of californium. However, from a range of spectroscopic techniques and quantum mechanical calculations, it is clear that spin-orbit coupling contributes significantly to berkelium's multiconfigurational ground state.

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Section: Discussionmentioning

confidence: 85%

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confidence: 99%

Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state

Silver

Cary

Johnson

et al. 2016

Science

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“…For the Pu−DOPO complex, the active space orbitals of the Pu-DOPO complex as determined from a CASSCF (9,12) calculation are presented in Figure S10. The sextet and quartet spin states are nearly degenerate (i.e., within 0.3 and 0.1 kcal/ mol using CASSCF and CASPT2, respectively (Table S11)).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…3−6 In one such study, tris(cyclopentadienyl) trivalent actinide systems were explored for 5f elements, extending all the way to californium; however, the characterization of these heavier actinide congeners is lacking. 7−11 Similarly, the dipicolinic acid (DPA) 12 and dithiocarbamate or phenanthroline 5 derivatives have been established, but those pertain only to the heavier actinides (Am−Cf) and omit the lighter derivatives.…”

Section: ■ Introductionmentioning

confidence: 99%

“…While this was predictable for the majority of this family, it was surprising to note that the californium derivative did not show increased covalency when bonding to the ligands, which is in contrast to previous reports of Cf(HDPA) 3 (HDPA = 2,6-pyridinedicarboxylate). 12 Given the lack of covalency in the trivalent system, our attention next turned to the lighter actinides. In contrast to the heavier actinides, the lighter actinides (Th−Pu) can access higher oxidation states more easily due to their increased reducing ability.…”

Section: ■ Introductionmentioning

confidence: 99%

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Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

et al. 2021

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Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium–ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

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Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes

et al. 2015

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The reaction of (248)CmCl3 with excess 2,6-pyridinedicarboxylic acid (DPA) under mild solvothermal conditions results in crystallization of the tris-chelate complex Cm(HDPA)3 · H2O. Approximately half of the curium remains in solution at the end of this process, and evaporation of the mother liquor results in crystallization of the bis-chelate complex [Cm(HDPA)(H2DPA)(H2O)2Cl]Cl·2H2O. (248)Cm is the daughter of the α decay of (252)Cf and is extracted in high purity from this parent. However, trace amounts of (249,250,251)Cf are still present in all samples of (248)Cm. During the crystallization of Cm(HDPA)3 · H2O and [Cm(HDPA)(H2DPA)(H2O)2Cl]Cl · 2H2O, californium(III) spontaneously separates itself from the curium complexes and is found doped within crystals of DPA in the form of Cf(HDPA)3. These results add to the growing body of evidence that the chemistry of californium is fundamentally different from that of earlier actinides.

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Californium gleaming

Cited by 3 publications

References 5 publications

Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state

Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state

Using Redox-Active Ligands to Generate Actinide Ligand Radical Species

Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes

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