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Synthesis and Characterization of Tris-chelate Complexes for Understanding <i>f</i>‑Orbital Bonding in Later Actinides

By Shane S. Galley (4803630), Scott A. Pattenaude (1573963), Carlo Alberto Gaggioli (1402807), Yusen Qiao (4910902), Joseph M. Sperling (4803636), Matthias Zeller (526374), Srimanta Pakhira (1448791), Jose L. Mendoza-Cortes (1288968), Eric J. Schelter (1317186), Thomas E. Albrecht-Schmitt (1370601), Laura Gagliardi (1279068) and Suzanne C. Bart (1360347)


An isostructural family of <i>f</i>-element compounds (Ce, Nd, Sm, Gd; Am, Bk, Cf) of the redox-active dioxophenoxazine ligand (DOPO<sup>q</sup>; DOPO = 2,4,6,8-tetra-<i>tert</i>-butyl-1-oxo-1<i>H</i>-phenoxazin-9-olate) was prepared. This family, of the form M­(DOPO<sup>q</sup>)<sub>3</sub>, represents the first nonaqueous isostructural series, including the later actinides berkelium and californium. The lanthanide derivatives were fully characterized using <sup>1</sup>H NMR spectroscopy and SQUID magnetometry, while all species were structurally characterized by X-ray crystallography and electronic absorption spectroscopy. In order to probe the electronic structure of this new family, CASSCF calculations were performed and revealed these systems to be largely ionic in contrast to previous studies, where berkelium and californium typically have a small degree of covalent character. To validate the zeroth order regular approximation (ZORA) method, the same CASSCF analysis using experimental structures versus UDFT-ZORA optimized structures does not exhibit sizable changes in bonding patterns. This shows that UDFT-ZORA combined with CASSCF could be a useful first approximation to predict and investigate the structure and electronic properties of actinides and lanthanides that are difficult to synthesize or characterize

Topics: Biophysics, Biochemistry, Medicine, Sociology, Plant Biology, Chemical Sciences not elsewhere classified, redox-active dioxophenoxazine ligand, UDFT-ZORA optimized structures, DOPO q, butyl -1-oxo H, covalent character, 1 H NMR spectroscopy, absorption spectroscopy, approximation, CASSCF analysis, californium, isostructural family, actinides berkelium, nonaqueous isostructural series, Tris-chelate Complexes, X-ray crystallography, element compounds, lanthanide derivatives, phenoxazin -9-olate, CASSCF calculations, SQUID magnetometry, zeroth order
Year: 2019
DOI identifier: 10.1021/jacs.8b10251.s005
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Provided by: FigShare
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