A series of dithiocarbamates for americium, curium, and californium

Abstract

Characterizing how actinide properties change across the f-element series is critical for improving predictive capabilities and solving many nuclear problems facing our society. Unfortunately, it is difficult to make direct comparisons across the 5f-element series because so little is known about trans-plutonium elements. Results described herein help to address this issue through isolation of An(S2CNEt2)3(N2C12H8) (Am, Cm, and Cf). These findings included the first single crystal X-ray diffraction measurements of Cm-S (mean of 2.86 ± 0.04 Å) and Cf-S (mean of 2.84 ± 0.04 Å) bond distances. Furthermore, they highlight the potential of An(S2CNEt2)3(N2C12H8) for providing a test bed for comparative analyses of actinide versus lanthanide bonding interactions.

Contemporary Chemistry of Berkelium and Californium

“…As confidence in our ability to synthesize late actinide molecules has increased, so has the complexity of the compounds that have been targeted. For example, phenanthroline dithiocarbamate complexes of Am III , Cm III , and Cf III with the general formula [An(dtc) 3 (phen)] (dtc=dithiocarbamate) have been prepared and thoroughly characterized . These compounds provide access to the first detailed understanding of trans‐plutonium bonding with sulfur‐based ligands.…”

“…This is al arger decrease in average bond length between Am III to Cf III than expected; the contraction between neighboring fe lements is usually on the order of 0.01 .T hese shorter bond lengths could be an indicator of increased effects of covalency across the series. [37,38,[62][63][64][65][66][67][68][69] Support for californium representing the location in the actinide series at which a second break occurs (the first being between plutonium and Figure 6. Californium borate luminescence (left) and magnetic susceptibility (right).…”

“…For example, phenanthroline dithiocarbamatec omplexes of Am III ,C m III ,a nd Cf III with the general formula [An(dtc) 3 (phen)] (dtc = dithiocarbamate) have been prepared and thoroughly characterized. [66] These compounds provide access to the first detailed understanding of trans-plutonium bonding with sulfur-based ligands. The compounds form an isotypic series of eight-coordinate An 3 + complexes.…”

“…Moreover,t he CfÀSb onds with am ean bond length of 2.84 are significantly shorter than other observed with either on An III cations or with Ln III cations that were previously thought to have similars ize. [66] As described above for [Bk(DOPO q ) 3 ], synthesis of the dtc complexes required the use of anhydrous solvents, but rigorous exclusion of water and air from the reactions was not essential. However,w hen extended to the [Cf(DOPO q ) 3 ]c omplex shown in Figure 7as ynthetic procedure similar to that of [Bk(DOPO q ) 3 ]n eeded to be employed.…”

Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour

“…[18] The importance of extending our experimental data based knowledget owards the trans-plutoniume lements was also demonstratedb yA lbrecht-Schmitt with the example of the dithiocarbamates of Am, Cm, and Cf. [19] Our presentw ork follows the same idea, dealing with homologous lanthanide and actinidec omplexes with the hydridotris(1-pyrazolyl)borato (Tp) ligand;t his work thus represents anothers tone in the mosaico fu nderstanding the differences and the commonalities of the lanthanidesa nd actinides.…”