Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

Journal Article · 05 February 2020 · Chemical Science

DOI: https://doi.org/10.1039/C9SC05268B · OSTI ID:1599242

Windorff, Cory J.  ^[1]; Celis-Barros, Cristian  ^[1]; Sperling, Joseph M.  ^[1]; McKinnon, Noah C. ^[1]; Albrecht-Schmitt, Thomas E.  ^[1]

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1. Florida State Univ., Tallahassee, FL (United States)

The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr₃(OPcy₃)₃, has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands display significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ~ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Florida State Univ., Tallahassee, FL (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0010677; SC0016568; FG02-13ER16414
• OSTI ID: 1599242
• Alternate ID(s): OSTI ID: 1767704; OSTI ID: 2370425
• Journal Information: Chemical Science, Vol. 11, Issue 10; ISSN 2041-6520
• Publisher: Royal Society of ChemistryCopyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
nuclear
defects
mechanical behavior
corrosion
charge transport
superconductivity
magnetism and spin physics
separations
geophysics/geochemistry
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (predictive)
synthesis (scalable processing)